Chemical agents capable of forming covalent 3-D networks

ABSTRACT

The invention provides a functionalized compound of formula (II), which functionalized compound comprises n carbene precursor groups which are the same or different, wherein n is an integer equal to or greater than 3: wherein x is 1, E is a group which is capable of being converted into a carbene reactive intermediate group, Q is a core moiety, a polymer or a dendrimer, and each of the [R] x -E-L- groups, which are the same or different, is independently selected from a group of formula (Ie) and a group of formula (Ia): wherein L is a single bond or a linker group as defined herein, R is a terminal group as defined herein, and R 1  is as defined herein. Further provided is the use of the functionalized compound as an agent for producing a chemically-bound three-dimensional network on or within a substrate. Processes for producing the following products using the functionalized compounds of the invention are also provided, as are the resulting products: a chemically-bound three-dimensional network on or within a substrate; a chemically-bound three-dimensional network between a first substrate and a second substrate; a film or a coating; a coated substrate; a product which comprises a first substrate, a second substrate and a composition at an interface of the first and second substrates; a treated particle. The invention further provides a process for cross linking a first substrate to a second substrate, using a functionalized compound of the invention, and the resulting cross-linked product. The invention also provides a process for producing the functionalized compounds of the invention.

CROSS-REFERENCE TO RELATED APPLICATION

This application is the national phase of PCT applicationPCT/GB2010/000368 having an international filing date of Mar. 2, 2010,which claims priority from European applications 0903563.5 filed Mar. 2,2009 and 0914692.9 filed Aug. 21, 2009. The contents of these documentsare incorporated herein by reference.

FIELD OF THE INVENTION

The invention relates to compounds (chemical agents) which are capableof forming extended 3-dimensional networks between multiple materials,coatings or substrates and to processes for producing such compounds.The invention further relates to the use of the compounds to alter thephysical and chemical nature of materials, to produce changes in therheological, thermal, cohesive and adhesive properties of materials, andto alter the molecular weight of a material. The invention furtherrelates the use of the compounds to produce particle-delivery compounds,to produce products in which two or more substrates or coatings areadhered, and to convert the rheological properties of a material.

BACKGROUND TO THE INVENTION

Modern technology and products are critically dependent on the use ofadvanced materials, including macroscopic materials, microscopicmaterials and nanomaterials, with properties carefully tailored to thedesired specific application. These properties can rarely be achievedwith one homogeneous material or compound, but are readily available byattaching one material or compound to another, giving a composite whoseproperties combine the desired properties of each component. Ofparticular importance is the control of thermal, rheological, cohesiveand adhesive properties as well as solvent resistance of materials. Suchproperties dictate the end application of material and limit the use ofa material in challenging environments. By the addition of a linkingagent which has the ability to interact with a material at two sites itis possible to influence these properties to a degree; examples of thiscan be found in JP59212832 or WO0158230. However since the interactionsfrom such agents are confined to two dimensions using this approach themagnitude of the change in properties is limited. Also, the examples arelimited to photo activation which precludes their use in manyapplications where the application of UV light is prevented, eitherbecause of sample stability, by ease of irradiation or by filmthickness/composition.

By creating a 3-dimensional network on or within a material via theaddition of a second chemical agent which is capable of forming stronginteractions (either physically or chemically) it is possible to producecomposites possessing hybrid properties and/or enhanced function. Suchmaterials find application in a wide variety of industries, includingfor instance the medical, chemical, hygiene, aeronautical, automotive,computing, and consumer product industries, for example as adhesives,composite matrix materials (carbon fibre, Kevlar, etc) and coatings.They are frequently used as components which are critical for thesuccessful function of a particular chemical product or device, or aschemical agents having an increased efficacy for a specific purpose.

There is therefore a continuing need to develop improved agents whichcan be used to form such three-dimensional networks, which can be usedwith a wide variety of substrates and materials, which offer safehandling in a production environment, and which possess curingconditions that are applicable for the market.

SUMMARY OF THE INVENTION

The inventors have provided a series of compounds which comprisemultiple functionalities. The functionalities are readily convertibleinto reactive intermediate carbene groups which can in turn react with awide variety of substrates, including individual compounds,nanoparticles, microparticles and bulk materials. Such functionalisedcompounds can be used as agents for creating 3-dimensional networkswithin a material or between materials for a wide variety ofapplications, for instance to produce products in which two or moresubstrates are adhered, to increase the thermal properties of coating,to alter the rheological properties of a material or to alter thechemical nature of a product such as in producing a particle-deliverycompound. The process for carrying out the network formation typicallyinvolves the use of a heat cure at a temperature which is low enough toallow the process to be carried out on a plastic or polymer substrate.Furthermore, in some embodiments of the invention a protected precursorto the reactive intermediate is employed which allows a greater level ofcontrol over unwanted degradation of the materials, such as in transportor storage.

Accordingly, the invention provides a functionalised compound of formula(II), which functionalised compound comprises n carbene precursor groupswhich are the same or different, wherein n is an integer equal to orgreater than 3:

wherein x is 1, E is a group which is capable of being converted into acarbene reactive intermediate group, Q is a core moiety, a polymer or adendrimer, and each of the [R]_(x)-E-L- groups, which are the same ordifferent, is independently selected from a group of formula (Ie) and agroup of formula (Ia):

wherein

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

R¹ is —S(O)₂R² or H, wherein R² is an unsubstituted or substituted C₁₋₆alkyl group or an unsubstituted or substituted aryl group;

-   -   with the proviso that when none of the [R]_(x)-E-L- groups is a        group of formula (Ie) in which R¹ is —S(O)₂R², then:        -   each L is a group of formula (XII); and        -   Q is a core moiety, a dendrimer, or a polymer, which polymer            comprises: a polysaccharide, a protein, a polyester, a            polyether, a polyacrylate, a polymethacrylate, a            polycarbonate, polyetheretherketone (PEEK), a            polyetherimide, a polyimide, a polysulfone, poly(vinyl            chloride), a polysilane, a polysiloxane, a polyurea, a            polyurethane, polylactic acid, polyvinylidene chloride, a            fluoro-polymer, a polyethylene imine, or a salt thereof.

In another aspect, the invention provides a process for producing achemically-bound three-dimensional network on or within a substrate,which process comprises:

(a) contacting a substrate with a functionalised compound of formula(II) of the invention as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the substrate to produce said chemically-boundthree-dimensional network on or within the substrate.

In another aspect, the invention provides a composition which comprisesa chemically-bound three-dimensional network on or within a substrate,the composition comprising:

-   -   (i) a substrate; and    -   (ii) a chemically-bound three-dimensional network on or within        the substrate, which chemically-bound three-dimensional network        is of formula (XXVIVa)

wherein

n is an integer equal to or greater than 3;

C is a carbon atom;

* is a point of attachment of the carbon atom to the substrate or toanother molecule or moiety in the composition;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ aryldi(C₁₋₂₀ diaryl(C₁₋₂₀ alkyl)silyl andtriarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a polymer or a dendrimer.

In another aspect, the invention provides a process for producing acomposition which comprises:

-   -   (i) a substrate; and    -   (ii) a chemically-bound three-dimensional network on or within        the substrate, which chemically-bound three-dimensional network        is of formula (XXVIVa)

wherein:

n is an integer equal to or greater than 3;

C is a carbon atom;

* is a point of attachment of the carbon atom to the substrate or toanother molecule or moiety in the composition;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a polymer or a dendrimer,

which process comprises:

(a) contacting a substrate with a functionalised compound of formula(II) of the invention as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the substrate to produce said composition.

In another aspect, the invention provides a process for producing achemically-bound three-dimensional network between a first substrate anda second substrate, which process comprises:

(a) contacting a first substrate and a second substrate with afunctionalised compound of formula (II) of the invention as definedherein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the first substrate and the second substrate to produce saidchemically-bound three-dimensional network between said first and secondsubstrates.

In another aspect, the invention provides a composition which comprises:

-   -   a first substrate;    -   a second substrate; and    -   a three-dimensional network of formula (XXVIVa), which is bound        to said first and second substrates:

wherein

n is an integer equal to or greater than 3;

C is a carbon atom;

* is a point of attachment of the carbon atom to the first or secondsubstrate or to another molecule or moiety in said composition;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ aryldi(C₁₋₂₀ diaryl(C₁₋₂₀ alkyl)silyl andtriarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a polymer or a dendrimer.

In another aspect, the invention provides a process for producing acomposition which comprises:

-   -   a first substrate;    -   a second substrate; and    -   a three-dimensional network of formula (XXVIVa):

wherein

n is an integer equal to or greater than 3;

C is a carbon atom;

* is a point of attachment of the carbon atom to the first or secondsubstrate or to another molecule or moiety in said composition;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a polymer or a dendrimer,

which process comprises:

(a) contacting a first substrate and a second substrate with afunctionalised compound of formula (II) of the invention as definedherein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the first substrate and the second substrate to produce saidcomposition.

In another aspect, the invention provides a process for producing a filmor a coating, which process comprises:

(a) disposing a film or coating formulation onto the surface of asubstrate, which film or coating formulation comprises a functionalisedcompound of formula (II) of the invention as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, thereby forming a film or a coating on said substrate.

In one embodiment, the process is for producing a film, and the processfurther comprises (c) removing said film from said substrate.

In another aspect, the invention provides a coated substrate whichcomprises:

-   -   a substrate; and    -   a coating on a surface of the substrate, which coating comprises        a three-dimensional network of formula (XXVIVa):

wherein

n is an integer equal to or greater than 3;

C is a carbon atom;

* is a point of attachment of the carbon atom to the substrate or toanother molecule or moiety in the coating;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)allylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a polymer or a dendrimer.

In another aspect, the invention provides a process for producing acoated substrate of the invention as defined above, comprises:

(a) disposing a coating formulation onto the surface of a substrate,which coating formulation comprises a functionalised compound of formula(II) of the invention as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, thereby forming a coating on said substrate.

In another aspect, the invention provides a product which comprises:

-   -   a first substrate;    -   a second substrate; and    -   a composition at an interface of the first and second        substrates, which composition comprises (i) a third material        and (ii) a three-dimensional network of formula (XXVIVa):

wherein

n is an integer equal to or greater than 3;

C is a carbon atom;

* is a point of attachment of the carbon atom to the first substrate,the second substrate, the third material, or to another molecule ormoiety in said composition at said interface of the first and secondsubstrates;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)allylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a polymer or a dendrimer.

In another aspect, the invention provides a process for producing aproduct of the invention as defined above, which process comprises:

(a) providing a composition at an interface of a first substrate and asecond substrate, which composition comprises (i) a third material and(ii) a functionalised compound of formula (II) of the invention asdefined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the first substrate, the second substrate, and the thirdmaterial, to produce said product.

In another aspect, the invention provides a process for producing atreated particle, which process comprises:

(a) contacting a functionalised cross linking compound with a substrateparticle, wherein the functionalised cross linking compound is acompound of formula (II) of the invention as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that a carbene reactive intermediate group reactswith the substrate particle to attach the particle to the compound,thereby yielding said particle-delivery compound.

The invention also provides a treated particle, which treated particlecomprises a substrate particle attached to a cross linking moiety offormula (XXVIVa):

wherein

n is an integer equal to or greater than 3;

C is a carbon atom;

* is a point of attachment of the carbon atom to the substrate particleor to another moiety or molecule;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a polymer or a dendrimer.

The treated particle of the invention may be used as a particle-deliverycompound. Accordingly, the treated particle may be termed aparticle-delivery compound.

In another aspect, the invention provides a process for cross linking afirst substrate to a second substrate, which first and second substratesare the same or different, which process comprises

(a) contacting the first and second substrates with a functionalisedcross linking compound, wherein the functionalised cross linkingcompound is a compound of formula (II) of the invention as definedherein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that at least one reactive intermediate groupreacts with the first substrate and at least one other reactiveintermediate group reacts with the second substrate, thereby crosslinking the first and second substrates.

In another aspect, the invention provides a cross-linked productcomprising:

(a) a first substrate;

(b) a second substrate; and

(c) a cross linking moiety of formula (XXVIVa):

wherein

n is an integer equal to or greater than 3;

C is a carbon atom;

* is a point of attachment of the carbon atom to the first substrate,the second substrate, or to another moiety or molecule;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ aryldi(C₁₋₂₀ alkyl)silyl, diaryl(C₁₋₂₀alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a polymer or a dendrimer.

In another aspect, the invention provides a process for producing afunctionalised compound of formula (II), which functionalised compoundcomprises n carbene precursor groups which are the same or different,wherein n is an integer equal to or greater than 3

wherein x is 1, E is a group which is capable of being converted into acarbene reactive intermediate group, Q is a core moiety, a polymer or adendrimer, and each of the [R]_(x)-E-L- groups, which are the same ordifferent, is independently selected from a group of formula (Ie) and agroup of formula (Ia):

wherein

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

R¹ is —S(O)₂R² or H, wherein R² is an unsubstituted or substituted C₁₋₆alkyl group or an unsubstituted or substituted aryl group;

-   -   with the proviso that when none of the [R]_(x)-E-L- groups is a        group of formula (Ie) in which R¹ is —S(O)₂R², then:        -   each L is a group of formula (XII); and        -   Q is a core moiety, a dendrimer, or a polymer, which polymer            comprises: a polysaccharide, a protein, a polyester, a            polyether, a polyacrylate, a polymethacrylate, a            polycarbonate, polyetheretherketone (PEEK), a            polyetherimide, a polyimide, a polysulfone, poly(vinyl            chloride), a polysilane, a polysiloxane, a polyurea, a            polyurethane, polylactic acid, polyvinylidene chloride, a            fluoro-polymer, a polyethylene imine, or a salt thereof;    -   which process comprises:        (a) treating a first compound, Q′, which is a core moiety, a        polymer or a dendrimer and which bears n functional groups, with        at least one second compound of formula (VIa)

wherein:

L′ is a leaving group or a reactive precursor to said group of formula(XII), wherein L′ is reactable with a said functional group to couplethe second compound to the first compound,

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are fluoroalkyl, C₁₋₂₀ perfluoroalkyl, aryl,cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy, haloalkyl,thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl, sulfonamide,tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl, diaryl(C₁₋₂₀alkyl)silyl and triarylsilyl, and

Y is N═N, O or N—NHR¹, wherein R¹ is H or —S(O)₂R² and wherein R² is anunsubstituted or substituted C₁₋₆ alkyl group or an unsubstituted orsubstituted aryl group,

provided that when none of the [R]_(x)-E-L- groups in the functionalisedcompound of formula (II) to be produced is a group of formula (Ie) inwhich R¹ is —S(O)₂R², then each L′ is a reactive precursor to said groupof formula (XII) and Q′ is a core moiety, a dendrimer, or a polymer,which polymer comprises: a polysaccharide, a protein, a polyester, apolyether, a polyacrylate, a polymethacrylate, a polycarbonate,polyetheretherketone (PEEK), a polyetherimide, a polyimide, apolysulfone, poly(vinyl chloride), a polysilane, a polysiloxane, apolyurea, a polyurethane, polylactic acid, polyvinylidene chloride, afluoro-polymer, a polyethylene imine, or a salt thereof;

thereby producing a third compound of formula (IXa):

wherein Q, L, R, Y and n are as defined above;

provided that:

-   -   when Y is O, the process further comprises:        (b) treating the third compound with H₂N—NHR¹ in the presence of        heat, wherein R¹ is as defined above, thereby producing a fourth        compound of formula (X):

wherein Q, L, R, R¹ and n are as defined above; and, optionally,(c) converting some or all of the N—NHR¹ groups of said fourth compoundinto diazo groups, N═N;

and provided that:

-   -   when Y is N—NHR¹, the process optionally further comprises:        (b) converting some or all of the Y groups of said third        compound into diazo groups;

thereby producing said functionalised compound of formula (II).

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic representation of the synthesis of triazine linkeddiazomethane locust bean gum.

FIG. 2 is a schematic representation of the synthesis of ether linkeddiazomethane locust bean gum.

FIG. 3 is a schematic representation of the attachment of triazine- andether-linked diazomethane locust bean gum compounds to perfumeencapsulates.

FIG. 4 is a schematic representation of the synthesis of tris(4-methyldiaryldiazomethane) 1,3,5-benzene triester.

FIG. 5 is a schematic representation of the synthesis of1,2,3-tri-O-(4-hydroxymethyl diaryl diazomethane-D,L-glyceryl ether.

FIG. 6 is a schematic representation of the synthesis of tosylhydrazone-functionalised polystyrene polymers and copolymers.

FIG. 7 is a fluorescence image which shows increased deposition ofencapsulates onto cotton using the functionalized compound of theinvention compared to a control experiment.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, a C₁₋₂₀ alkyl group is an unsubstituted or substituted,straight or branched chain saturated hydrocarbon radical having from 1to 20 carbon atoms. Typically it is C₁₋₁₀ alkyl, for example methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, orC₁₋₆ alkyl, for example methyl, ethyl, propyl, butyl, pentyl or hexyl,or C₁₋₄ alkyl, for example methyl, ethyl, i-propyl, n-propyl, t-butyl,s-butyl or n-butyl. In one embodiment, it is a C₂₋₂₀ alkyl group or, forinstance, a C₃₋₂₀ alkyl or a C₄₋₂₀ alkyl group. When an alkyl group issubstituted it typically bears one or more (e.g. one, two, three orfour) substituents selected from substituted or unsubstituted C₁₋₂₀alkyl; substituted or unsubstituted C₂₋₂₀ alkenyl; substituted orunsubstituted C₂₋₂₀ alkynyl; substituted or unsubstituted aryl;substituted or unsubstituted aralkyl; halo; cyano; keto; amino; C₁₋₁₀alkylamino; di(C₁₋₁₀)allylamino; arylamino; diarylamino; arylalkylamino;amido; acylamido; C₁₋₂₀ haloalkyl (e.g. —CF₃); ester; acyl; acyloxy;C₁₋₁₀ alkoxy; aryloxy; nitro; hydroxyl, carboxy; sulfonic acid;sulfonyl; sulphonamide; sulfhydryl (i.e. thiol, —SH); C₁₋₁₀ alkylthio;arylthio; tri(C₁₋₂₀ alkyl)silyl; aryldi(C₁₋₂₀ alkyl)silyl; diaryl(C₁₋₂₀alkyl)silyl; and triarylsilyl.

Examples of substituted alkyl groups include C₁₋₂₀ haloalkyl,alkoxyalkyl and alkaryl groups. The term alkaryl, as used herein,pertains to a C₁₋₂₀ alkyl group in which at least one hydrogen atom(e.g., 1, 2, 3) has been replaced with an aryl group. Examples of suchgroups include, but are not limited to, benzyl (phenylmethyl, PhCH₂—),benzhydryl (Ph₂CH—), trityl (triphenylmethyl, Ph₃C—), phenethyl(phenylethyl, Ph-CH₂CH₂—), styryl (Ph-CH═CH—), cinnamyl (Ph-CH═CH—CH₂—).

Typically a substituted C₁₋₂₀ alkyl group carries 1, 2 or 3substituents, for instance 1 or 2.

A C₁₋₂₀ haloalkyl group is a straight or branched chain saturated C₁₋₂₀alkyl group in which at least one hydrogen atom has been replaced with ahalogen atom, typically F, Cl or Br. In a C_(n) haloalkyl group, where nis from 1 to 20, the number of hydrogen atoms replaced with a halogenatom may be from n to (2n+1). The halogen atoms may be the same ordifferent. C₁₋₂₀ haloalkyl groups include C₁₋₂₀ fluoroalkyl groups andC₁₋₂₀ perfluoroalkyl groups, as defined below. A C₁₋₂₀ haloalkyl groupmay have at least two halogen atoms or, for instance, at least threehalogen atoms.

A C₁₋₂₀ fluoroalkyl group is a straight or branched chain saturatedC₁₋₂₀ alkyl group in which at least one hydrogen atom has been replacedwith a fluorine atom. In a C_(n) fluoroalkyl group, where n is from 1 to20, the number of hydrogen atoms replaced with a fluorine atom may befrom n to (2n+1). Thus, C₁₋₂₀ fluoroalkyl groups include C₁₋₂₀perfluoroalkyl groups, in which all the hydrogen atoms that wouldotherwise have been present are replaced with a fluorine atom.Typically, a C₁₋₂₀ fluoroalkyl group has at least two fluorine atoms,more typically at least three fluorine atoms. Typically a C₁₋₂₀fluoroalkyl group is a C₂₋₂₀ fluoroalkyl group, or for instance a C₃₋₂₀fluoroalkyl group. Typically, a C₂₋₂₀ fluoroalkyl group has at leastthree fluorine atoms, more typically at least four fluorine atoms.Typically, a C₃₋₂₀ fluoroalkyl group has at least three fluorine atoms,more typically at least four fluorine atoms or, for instance, at leastsix fluorine atoms.

A C₁₋₂₀ perfluoroalkyl group is a straight or branched chain saturatedperfluorinated hydrocarbon radical having from 1 to 20 carbon atoms.“Perfluorinated” in this context means completely fluorinated such thatthere are no carbon-bonded hydrogen atoms replaceable with fluorine.Typically it is C₁₋₁₂ perfluoroalkyl, for example trifluoromethyl (C₁),pentafluoroethyl (C₂), perfluoropropyl (C₃) (includingperfluoro-n-propyl and perfluoro-iso-propyl), perfluorobutyl (C₄)(including perfluoro-n-butyl, perfluoro-iso-butyl, perfluoro-sec-butyland perfluoro-tert-butyl), perfluoropentyl (C₅), perfluorohexyl (C₆),perfluoroheptyl (C₇), perfluorooctyl (C₈), perfluorononyl (C₉),perfluorodecyl (C₁₀), perfluoroundecyl (C₁₁) and perfluorododecyl (C₁₂),including straight chained and branched isomers thereof.

A C₁₋₂₀ hydrocarbon moiety is a straight-chained or branched, saturatedor unsaturated hydrocarbon moiety having from 1 to 20 carbon atoms. AC₁₋₂₀ hydrocarbon moiety may be unsubstituted or substituted, thesubstituents, unless otherwise specified, being selected from thoselisted above for C₁₋₂₀ alkyl groups. Typically, when a C₁₋₂₀ hydrocarbonmoiety is substituted, it is substituted by from one to four (e.g. one,two, three or four) substituents.

A tri(C₁₋₂₀ alkyl)silyl group represents a group of formula:—Si(R′)(R″)(R′″) wherein R′, R″ and R′″, which are the same ordifferent, are unsubstituted or substituted, straight or branched chainC₁₋₂₀ alkyl groups as defined above.

A aryldi(C₁₋₂₀ alkyl)silyl group represents a group of formula:—Si(R′)(R″)(R′″) wherein R′ and R″, which are the same or different, areunsubstituted or substituted, straight or branched chain C₁₋₂₀ alkylgroups as defined above, and wherein R′″ is an unsubstituted orsubstituted aryl group.

A diaryl(C₁₋₂₀ alkyl)silyl group represents a group of formula:—Si(R′)(R″)(R′″) wherein R′ is an unsubstituted or substituted, straightor branched chain C₁₋₂₀ alkyl group as defined above, and wherein R″ andR′″, which are the same or different, are unsubstituted or substitutedaryl groups.

A triarylsilyl group represents a group of formula: —Si(R′)(R″)(R′″)wherein R′, R″ and R′″, which are the same or different, areunsubstituted or substituted aryl groups.

A C₂₋₂₀ alkenyl group is a straight or branched group, which containsfrom 2 to 20 carbon atoms. One or more double bonds may be present inthe alkenyl group, typically one double bond. A C₂₋₂₀ alkenyl group istypically ethenyl or a C₃₋₁₀ alkenyl group, i.e. a C₂₋₁₀ alkenyl group,more typically a C₂₋₆ alkenyl group. A C₃₋₁₀ alkenyl group is typicallya C₃₋₆ alkenyl group, for example allyl, propenyl, butenyl, pentenyl orhexenyl. A C₂₋₄ alkenyl group is ethenyl, propenyl or butenyl. Analkenyl group may be unsubstituted or substituted by one to four (e.g.one, two, three or four) substituents, the substituents, unlessotherwise specified, being selected from those listed above for C₁₋₂₀alkyl groups. Where two or more substituents are present, these may bethe same or different.

A C₂₋₂₀ alkynyl group is a straight or branched group which, unlessotherwise specified, contains from 2 to 20 carbon atoms. One or moretriple bonds, and optionally one or more double bonds may be present inthe alkynyl group, typically one triple bond. A C₂₋₂₀ alkynyl group istypically ethynyl or a C₃₋₁₀ alkynyl group, i.e. a C₂₋₁₀ alkynyl group,more typically a C₂₋₆ alkynyl group. A C₃₋₁₀ alkynyl group is typicallya C₃₋₆ alkynyl group, for example propynyl, butynyl, pentynyl orhexynyl. A C₂₋₄ alkynyl group is ethynyl, propynyl or butynyl. Analkynyl group may be unsubstituted or substituted by one to foursubstituents (e.g. one, two, three or four), the substituents, unlessotherwise specified, being selected from those listed above for C₁₋₂₀alkyl groups. Where two or more substituents are present, these may bethe same or different.

An aryl ring is an unsubstituted or substituted aromatic ring ofcovalently linked carbon atoms. Typically, the aryl ring is a 5- or6-membered aryl ring, examples of which include cyclopentadienyl (C_(p))and phenyl. An aryl ring may be unsubstituted or substituted by,typically, one to five substituents (e.g. one, two, three, four orfive), the substituents, unless otherwise specified, being selected fromthose listed above for C₁₋₂₀ alkyl groups. Where two or moresubstituents are present, these may be the same or different.

A heteroaryl ring is an unsubstituted or substituted heteroaromatic ringof covalently linked atoms including one or more heteroatoms. The one ormore heteroatoms are typically selected from nitrogen, phosphorus,silicon, oxygen and sulfur (more commonly from nitrogen, oxygen andsulfur). A heteroaryl ring is typically a 5- or 6-membered heteroarylring containing at least one heteroatom selected from nitrogen,phosphorus, silicon, oxygen and sulfur (more commonly selected fromnitrogen, oxygen and sulfur). It may contain, for example, 1, 2 or 3heteroatoms. Examples of heteroaryl rings include pyridine, pyrazine,pyrimidine, pyridazine, furan, thiofuran, pyrazole, pyrrole, oxazole,oxadiazole, isoxazole, thiadiazole, thiazole, isothiazole, imidazole andpyrazole. A heteroaryl ring may be unsubstituted or substituted by,typically, one to four substituents (e.g. one, two, three or four), thesubstituents, unless otherwise specified, being selected from thoselisted above for C₁₋₂₀ alkyl groups. Where two or more substituents arepresent, these may be the same or different.

A C₅₋₁₀ carbocyclic ring is an unsubstituted or substituted closed ringof from 5 to 10 covalently linked carbon atoms, which ring is saturatedor unsaturated. Typically, the C₅₋₁₀ carbocyclic ring is not an aromaticring. Typically the C₅₋₁₀ carbocyclic ring is a C₅₋₆ carbocyclic ring.The carbocyclic ring may be saturated or unsaturated. Thus, the termC₅₋₁₀ carbocyclic ring includes the sub-classes C₅₋₁₀ cycloalkyl ring,C₅₋₁₀ cycloalkyenyl ring and C₅₋₁₀ cycloalkynyl ring. When a C₅₋₁₀carbocyclic ring is substituted it typically bears one or moresubstituents selected from those listed above for C₁₋₂₀ alkyl groups.Examples of C₅₋₁₀ carbocyclic rings include, but are not limited to:

cyclopentane (C₅), cyclohexane (C₆), cycloheptane (C₇),methylcyclopropane (C₄), dimethylcyclopropane (C₅), methylcyclobutane(C₅), dimethylcyclobutane (C₆), methylcyclopentane (C₆),dimethylcyclopentane (C₇), methylcyclohexane (C₇), dimethylcyclohexane(C₈), menthane (C₁₀), cyclopentene (C₅), cyclopentadiene (C₅),cyclohexene (C₆), cyclohexadiene (C₆), methylcyclopropene (C₄),dimethylcyclopropene (C₅), methylcyclobutene (C₅), dimethylcyclobutene(C₆), methylcyclopentene (C₆), dimethylcyclopentene (C₇),methylcyclohexene (C₇), dimethylcyclohexene (C₈).

A C₅₋₁₀ heterocyclic ring is an unsubstituted or substituted closed ringof from 5 to 10 covalently linked atoms, which ring is saturated orunsaturated, wherein at least one of the ring atoms is a multivalentring heteroatom, for example, nitrogen, phosphorus, silicon, oxygen, orsulfur (though more commonly nitrogen, oxygen, or sulfur). Typically,the C₅₋₁₀ heterocyclic ring is not an aromatic ring. Typically, theC₅₋₁₀ heterocyclic ring has from 1 to 4 heteroatoms, the remainder ofthe ring atoms are carbon. Typically, the C₅₋₁₀ heterocyclic ring is aC₅₋₆ heterocyclic ring in which from 1 to 4 of the ring atoms are ringheteroatoms, and the remainder of the ring atoms are carbon atoms. Inthis context, the prefixes C₅₋₁₀ and C₅₋₆ denote the number of ringatoms, or range of number of ring atoms. When a C₅₋₁₀ heterocyclic ringis substituted it typically bears one or more substituents selected fromthose listed above for C₁₋₂₀ alkyl groups.

Examples of monocyclic C₅₋₁₀ heterocyclic rings include, but are notlimited to:

N₁: pyrrolidine (tetrahydropyrrole) (C₅), pyrroline (e.g., 3-pyrroline,2,5-dihydropyrrole) (C₅), 2H-pyrrole or 3H-pyrrole (isopyrrole,isoazole) (C₅), piperidine (C₆), dihydropyridine (C₆),tetrahydropyridine (C₆), azepine (C₇);

O₁: oxolane (tetrahydrofuran) (C₅), oxole (dihydrofuran) (C₅), oxane(tetrahydropyran) (C₆), dihydropyran (C₆), pyran (C₆), oxepin (C₇);

S₁: thiolane (tetrahydrothiophene) (C₅), thiane (tetrahydrothiopyran)(C₆), thiepane (C₇);

O₂: dioxolane (C₅), dioxane (C₆), and dioxepane (C₇);

O₃: trioxane (C₆);

N₂: imidazolidine (C₅), pyrazolidine (diazolidine) (C₅), imidazoline(C₅), pyrazoline (dihydropyrazole) (C₅), piperazine (C₆);

N₁O₁: tetrahydrooxazole (C₅), dihydrooxazole (C₅), tetrahydroisoxazole(C₅), dihydroisoxazole (C₅), morpholine (C₆), tetrahydrooxazine (C₆),dihydrooxazine (C₆), oxazine (C₆);

N₁S₁: thiazoline (C₅), thiazolidine (C₅), thiomorpholine (C₆);

N₂O₁: oxadiazine (C₆);

O₁S₁: oxathiole (C₅) and oxathiane (thioxane) (C₆); and,

N₁O₁S₁: oxathiazine (C₆).

A C₃₋₂₀ carbocyclyl group is an unsubstituted or substituted monovalentmoiety obtained by removing a hydrogen atom from an alicyclic ring atomof a carbocyclic ring of a carbocyclic compound, which moiety has from 3to 20 carbon atoms (unless otherwise specified), including from 3 to 20ring atoms. The carbocyclyl ring may be saturated or unsaturated. Thus,the term “carbocyclyl” includes the sub-classes cycloalkyl,cycloalkyenyl and cycloalkynyl. Preferably, each ring has from 5 to 7ring atoms. Examples of groups of C₃₋₂₀ carbocyclyl groups include C₃₋₁₀carbocyclyl, C₅₋₇ carbocyclyl and C₅₋₆ carbocyclyl. When a C₃₋₂₀carbocyclyl group is substituted it typically bears one or moresubstituents (typically one, two, three or four substituents) selectedfrom those listed above for C₁₋₂₀ alkyl groups.

Examples of C₃₋₂₀ carbocyclyl groups include, but are not limited to,those derived from saturated monocyclic hydrocarbon compounds:

cyclopropane (C₃), cyclobutane (C₄), cyclopentane (C₅), cyclohexane(C₆), cycloheptane (C₇), methylcyclopropane (C₄), dimethylcyclopropane(C₅), methylcyclobutane (C₅), dimethylcyclobutane (C₆),methylcyclopentane (C₆), dimethylcyclopentane (C₇), methylcyclohexane(C₇), dimethylcyclohexane (C₈), menthane (C₁₀);

unsaturated monocyclic hydrocarbon compounds:

cyclopropene (C₃), cyclobutene (C₄), cyclopentene (C₅), cyclopentadiene(C₅), cyclohexene (C₆), cyclohexadiene (C₆), methylcyclopropene (C₄),dimethylcyclopropene (C₅), methylcyclobutene (C₅), dimethylcyclobutene(C₆), methylcyclopentene (C₆), dimethylcyclopentene (C₇),methylcyclohexene (C₇), dimethylcyclohexene (C₈);

saturated polycyclic hydrocarbon compounds:

thujane (C₁₀), carane (C₁₀), pinane (C₁₀), bornane (C₁₀), norcarane(C₇), norpinane (C₇), norbornane (C₇), adamantane (C₁₀), decalin(decahydronaphthalene) (C₁₀); unsaturated polycyclic hydrocarboncompounds: camphene (C₁₀), limonene (C₁₀), pinene (C₁₀);

polycyclic hydrocarbon compounds having an aromatic ring:

indene (C₉), indane (e.g., 2,3-dihydro-1H-indene) (C₉), tetraline(1,2,3,4-tetrahydronaphthalene) (C₁₀), acenaphthene (C₁₂), fluorene(C₁₃), phenalene (C₁₃), 5,5,8,8-tetramethyl tetraline (C₁₄),acephenanthrene (C₁₅), aceanthrene (C₁₆), cholanthrene (C₂₀).

Further examples of C₃₋₂₀ carbocyclyl groups include C₃₋₂₀halocarbocyclyl groups, C₃₋₂₀ fluorocarbocyclyl groups, C₃₋₂₀perfluorocarbocyclyl groups and C₃₋₁₀ cycloalkyl groups.

A C₃₋₂₀ halocarbocyclyl group is a C₃₋₂₀ carbocyclyl group in which atleast one hydrogen atom has been replaced with a halogen atom, typicallyF, Cl or Br. The halogen atoms may be the same or different. C₃₋₂₀halocarbocyclyl groups include C₃₋₂₀ fluorocarbocyclyl groups and C₃₋₂₀perfluorocarbocyclyl groups, as defined below. A C₃₋₂₀ halocarbocyclylgroup may have at least two halogen atoms or, for instance, at leastthree or at least four, at least five or at least six halogen atoms.

A C₃₋₂₀ fluorocarbocyclyl group is a C₃₋₂₀ carbocyclyl group in which atleast one hydrogen atom has been replaced with a fluorine atom. C₃₋₂₀fluorocarbocyclyl groups include C₃₋₂₀ perfluorocarbocyclyl groups, asdefined below. A C₃₋₂₀ fluorocarbocyclyl group may have at least twofluorine atoms or, for instance, at least three or at least four, atleast five or at least six fluorine atoms.

A C₃₋₂₀ perfluorocarbocyclyl group a perfluorinated C₃₋₂₀ carbocyclylgroup. “Perfluorinated” in this context means completely fluorinatedsuch that there are no carbon-bonded hydrogen atoms replaceable withfluorine.

A C₃₋₁₀ cycloalkyl group or moiety is a 3- to 10-membered unsubstitutedor substituted group or moiety, typically a 3- to 6-membered group ormoiety, which may be a monocyclic ring or which may consist of two ormore fused rings. Examples of C₃₋₁₀ cycloalkyl groups or moietiesinclude cyclopropane (C₃), cyclobutane (C₄), cyclopentane (C₅),cyclohexane (C₆), cycloheptane (C₇), methylcyclopropane (C₄),dimethylcyclopropane (C₅), methylcyclobutane (C₅), dimethylcyclobutane(C₆), methylcyclopentane (C₆), dimethylcyclopentane (C₇),methylcyclohexane (C₇), dimethylcyclohexane (C₈), menthane (C₁₀),thujane (C₁₀), carane (C₁₀), pinane (C₁₀), bornane (C₁₀), norcarane(C₇), norpinane (C₇), norbornane (C₇), adamantane (C₁₀) and decalin(decahydronaphthalene) (C₁₀).

A C₃₋₂₀ heterocyclyl group is an unsubstituted or substitutedmonovalent, monocyclic, bicyclic or tricyclic moiety obtained byremoving a hydrogen atom from a ring atom of a heterocyclic compound,which moiety has from 3 to 20 ring atoms (unless otherwise specified),of which from 1 to 10 are ring heteroatoms. Preferably, each ring hasfrom 3 to 7 ring atoms, of which from 1 to 4 are ring heteroatoms. Whena C₃₋₂₀ heterocyclyl group is substituted it typically bears one or moresubstituents selected from those listed above for C₁₋₂₀ alkyl groups.Typically a substituted C₃₋₂₀ heterocyclyl group carries 1, 2 or 3substituents, for instance 1 or 2.

Examples of groups of heterocyclyl groups include C₃₋₂₀ heterocyclyl,C₅₋₂₀ heterocyclyl, C₃₋₁₅ heterocyclyl, C₅₋₁₅ heterocyclyl, C₃₋₁₂heterocyclyl, C₅₋₁₂ heterocyclyl, C₃₋₁₀ heterocyclyl, C₅₋₁₀heterocyclyl, C₃₋₇ heterocyclyl, C₅₋₇ heterocyclyl, and C₅₋₆heterocyclyl.

Examples of monocyclic C₃₋₂₀ heterocyclyl groups include, but are notlimited to, those derived from:

N₁: aziridine (C₃), azetidine (C₄), pyrrolidine (tetrahydropyrrole)(C₅), pyrroline (e.g., 3-pyrroline, 2,5-dihydropyrrole) (C₅), 2H-pyrroleor 3H-pyrrole (isopyrrole, isoazole) (C₅), piperidine (C₆),dihydropyridine (C₆), tetrahydropyridine (C₆), azepine (C₇);

O₁: oxirane (C₃), oxetane (C₄), oxolane (tetrahydrofuran) (C₅), oxole(dihydrofuran) (C₅), oxane (tetrahydropyran) (C₆), dihydropyran (C₆),pyran (C₆), oxepin (C₇);

S₁: thiirane (C₃), thietane (C₄), thiolane (tetrahydrothiophene) (C₅),thiane (tetrahydrothiopyran) (C₆), thiepane (C₇);

O₂: dioxolane (C₅), dioxane (C₆), and dioxepane (C₇);

O₃: trioxane (C₆);

N₂: imidazolidine (C₅), pyrazolidine (diazolidine) (C₅), imidazoline(C₅), pyrazoline (dihydropyrazole) (C₅), piperazine (C₆);

N₁O₁: tetrahydrooxazole (C₅), dihydrooxazole (C₅), tetrahydroisoxazole(C₅), dihydroisoxazole (C₅), morpholine (C₆), tetrahydrooxazine (C₆),dihydrooxazine (C₆), oxazine (C₆);

N₁S₁: thiazoline (C₅), thiazolidine (C₅), thiomorpholine (C₆);

N₂O₁: oxadiazine (C₆);

O₁S₁: oxathiole (C₅) and oxathiane (thioxane) (C₆); and,

N₁O₁S₁: oxathiazine (C₆).

Examples of C₃₋₂₀ heterocyclyl groups which are also aryl groups aredescribed below as heteroaryl groups.

An aryl group is a substituted or unsubstituted, monocyclic or bicyclicaromatic group which typically contains from 6 to 14 carbon atoms,preferably from 6 to 10 carbon atoms in the ring portion. Examplesinclude phenyl, naphthyl, indenyl and indanyl groups. An aryl group isunsubstituted or substituted. When an aryl group as defined above issubstituted it typically bears one or more substituents (for instance,one, two, three, four or five substituents) selected from those listedabove for C₁₋₂₀ alkyl groups. A substituted aryl group may besubstituted in two positions with a single unsubstituted or substitutedC₁₋₆ alkylene group, or with a bidentate group represented by theformula —X—C₁₋₆ alkylene, or —X—C₁₋₆ alkylene-X—, wherein X is selectedfrom O, S and NR, and wherein R is H, aryl or C₁₋₆ alkyl. Thus asubstituted aryl group may be an aryl group fused with a cycloalkylgroup or with a heterocyclyl group. A further example of a substitutedaryl group is a C₆₋₁₀ perfluoroaryl group.

A C₆₋₁₀ perfluoroaryl group is a perfluorinated aryl group whichcontains from 6 to 10 carbon atoms in the ring portion. “Perfluorinated”in this context means completely fluorinated such that there are nocarbon-bonded hydrogen atoms replaceable with fluorine. Typically it ispentafluorophenyl.

The term aralkyl as used herein, pertains to an aryl group in which atleast one hydrogen atom (e.g., 1, 2, 3) has been substituted with aC₁₋₂₀ alkyl group. Examples of such groups include, but are not limitedto, tolyl (from toluene), xylyl (from xylene), mesityl (frommesitylene), and cumenyl (or cumyl, from cumene), and duryl (fromdurene).

The ring atoms of an aryl group may include one or more heteroatoms, asin a heteroaryl group. Such an aryl group (a heteroaryl group) is asubstituted or unsubstituted mono- or bicyclic heteroaromatic groupwhich typically contains from 6 to 10 atoms in the ring portionincluding one or more heteroatoms. It is generally a 5- or 6-memberedring, or two fused rings each of which is the same or different andtypically independently selected from a 5-membered ring and a 6-memberedring, containing at least one heteroatom selected from O, S, N, P, Seand Si. It may contain, for example, 1, 2 or 3 heteroatoms. Examples ofheteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl,furanyl, thienyl, pyrazolidinyl, pyrrolyl, oxazolyl, oxadiazolyl,isoxazolyl, thiadiazolyl, thiazolyl, isothiazolyl, imidazolyl,pyrazolyl, quinolyl and isoquinolyl. A heteroaryl group may beunsubstituted or substituted, for instance, as specified above for aryl.Typically it carries 0, 1, 2 or 3 substituents.

A C₁₋₂₀ alkylene group is an unsubstituted or substituted bidentatemoiety obtained by removing two hydrogen atoms, either both from thesame carbon atom, or one from each of two different carbon atoms, of ahydrocarbon compound having from 1 to 20 carbon atoms (unless otherwisespecified), which may be aliphatic or alicyclic, and which may besaturated, partially unsaturated, or fully unsaturated. Thus, the term“alkylene” includes the sub-classes alkenylene (C₁₋₂₀ alkenylene),alkynylene (C₁₋₂₀ alkynylene), cycloalkylene, etc. Typically it is C₁₋₁₀alkylene, or C₁₋₆ alkylene. Typically it is C₁₋₄ alkylene, for examplemethylene, ethylene, i-propylene, n-propylene, t-butylene, s-butylene orn-butylene. It may also be pentylene, hexylene, heptylene, octylene andthe various branched chain isomers thereof. An alkylene group may beunsubstituted or substituted, for instance, as specified above foralkyl. Typically a substituted alkylene group carries 1, 2 or 3substituents, for instance 1 or 2.

In this context, the prefixes (e.g., C₁₋₄, C₁₋₇, C₁₋₁₀, C₂₋₇, C₃₋₇,etc.) denote the number of carbon atoms, or range of number of carbonatoms. For example, the term “C₁₋₄ alkylene,” as used herein, pertainsto an alkylene group having from 1 to 4 carbon atoms. Examples of groupsof alkylene groups include C₁₋₄ alkylene (“lower alkylene”), C₁₋₇alkylene and C₁₋₁₀ alkylene.

Examples of linear saturated C₁₋₇ alkylene groups include, but are notlimited to, —(CH₂)_(n)— where n is an integer from 1 to 7, for example,—CH₂— (methylene), —CH₂CH₂— (ethylene), —CH₂CH₂CH₂— (propylene), and—CH₂CH₂CH₂CH₂— (butylene).

Examples of branched saturated C₁₋₇ alkylene groups include, but are notlimited to, —CH(CH₃)—, —CH(CH₃)CH₂—, —CH(CH₃)CH₂CH₂—,—CH(CH₃)CH₂CH₂CH₂—, —CH₂CH(CH₃)CH₂—, —CH₂CH(CH₃)CH₂CH₂—, —CH(CH₂CH₃)—,—CH(CH₂CH₃)CH₂—, and —CH₂CH(CH₂CH₃)CH₂—.

Examples of linear partially unsaturated C₁₋₇ alkylene groups include,but is not limited to, —CH═CH— (vinylene), —CH═CH—CH₂—, —CH₂—CH═CH₂—,—CH═CH—CH₂—CH₂—, —CH═CH—CH₂—CH₂—CH₂—, —CH═CH—CH═CH—, —CH═CH—CH═CH—CH₂—,—CH═CH—CH═CH—CH₂—CH₂—, —CH═CH—CH₂—CH═CH—, and —CH═CH—CH₂—CH₂—CH═CH—.

Examples of branched partially unsaturated C₁₋₇ alkylene groups include,but is not limited to, —C(CH₃)═CH—, —C(CH₃)═CH—CH₂—, and—CH═CH—CH(CH₃)—.

Examples of alicyclic saturated C₁₋₇ alkylene groups include, but arenot limited to, cyclopentylene (e.g., cyclopent-1,3-ylene), andcyclohexylene (e.g., cyclohex-1,4-ylene).

Examples of alicyclic partially unsaturated C₁₋₇ alkylene groupsinclude, but are not limited to, cyclopentenylene (e.g.,4-cyclopenten-1,3-ylene), cyclohexenylene (e.g., 2-cyclohexen-1,4-ylene;3-cyclohexen-1,2-ylene; 2,5-cyclohexadien-1,4-ylene). These are examplesof C₅₋₆ cycloalkylene groups.

An example of a substituted C₁₋₂₀ alkylene group is a C₁₋₂₀perfluoroalkylene group. A C₁₋₂₀ perfluoroalkylene group is aperfluorinated C₁₋₂₀ alkylene group. “Perfluorinated” in this contextmeans completely fluorinated such that there are no carbon-bondedhydrogen atoms replaceable with fluorine.

C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, C₁₋₂₀ alkyl, C₁₋₂₀ haloalkyl,C₁₋₂₀ fluoroalkyl and C₁₋₂₀ perfluoroalkyl groups as defined herein areeither uninterrupted or interrupted by one or more heteroatoms orheterogroups, such as S, O or N(R″) wherein R″ is H, C₁₋₆ alkyl or aryl(typically phenyl), or by one or more arylene groups. The arylene groupsare typically phenylene, but may be perfluoroarylene groups, forinstance tetrafluorophenylene. The phrase “optionally interrupted” asused herein thus refers to a C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene,C₁₋₂₀ alkyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl or C₁₋₂₀ perfluoroalkylgroup, as defined above, which is uninterrupted or which is interruptedbetween adjacent carbon atoms by a heteroatom such as oxygen or sulfur,by a heterogroup such as N(R″) wherein R″ is H, aryl or C₁₋₆ alkyl, orby an arylene group. For instance, a C₁₋₂₀ alkyl group such as n-butylmay be interrupted by the heterogroup N(R″) as follows:—CH₂N(R″)CH₂CH₂CH₃, —CH₂CH₂N(R″)CH₂CH₃, or —CH₂CH₂CH₂N(R″)CH₃.Similarly, an alkylene group such as n-butylene may be interrupted bythe heterogroup N(R″) as follows: —CH₂N(R″)CH₂CH₂CH₂—,—CH₂CH₂N(R″)CH₂CH₂—, or —CH₂CH₂CH₂N(R″)CH₂—. Typically an interruptedgroup, for instance an interrupted C₁₋₁₀ alkylene or C₁₋₂₀ alkyl group,is interrupted by 1, 2 or 3 heteroatoms or heterogroups, or by 1, 2 or 3arylene (typically phenylene) groups. More typically, an interruptedgroup, for instance an interrupted C₁₋₁₀ alkylene or C₁₋₂₀ alkyl group,is interrupted by 1 or 2 heteroatoms or heterogroups, or by 1 or 2arylene (typically phenylene) groups. For instance, a C₁₋₂₀ alkyl groupsuch as n-butyl may be interrupted by 2 heterogroups N(R″) as follows:—CH₂N(R″)CH₂N(R″)CH₂CH₃.

An arylene group is an unsubstituted or substituted bidentate moietyobtained by removing two hydrogen atoms, one from each of two differentaromatic ring atoms of an aromatic compound, which moiety has from 5 to14 ring atoms (unless otherwise specified). Typically, each ring hasfrom 5 to 7 or from 5 to 6 ring atoms. An arylene group may beunsubstituted or substituted, for instance, as specified above for aryl.Typically a substituted heteroarylene group carries 1, 2 or 3substituents, for instance 1 or 2.

In this context, the prefixes (e.g., C₅₋₂₀, C₆₋₂₀, C₅₋₁₄, C₅₋₇, C₅₋₆,etc.) denote the number of ring atoms, or range of number of ring atoms,whether carbon atoms or heteroatoms. For example, the term “C₅₋₆arylene,” as used herein, pertains to an arylene group having 5 or 6ring atoms. Examples of groups of arylene groups include C₅₋₂₀ arylene,C₆₋₂₀ arylene, C₅₋₁₄ arylene, C₆₋₁₄ arylene, C₆₋₁₀ arylene, C₅₋₁₂arylene, C₅₋₁₀ arylene, C₅₋₇ arylene, C₅₋₆ arylene, C₅ arylene, and C₆arylene.

The ring atoms may be all carbon atoms, as in “carboarylene groups”(e.g., C₆₋₂₀ carboarylene, C₆₋₁₄ carboarylene or C₆₋₁₀ carboarylene).

Examples of C₆₋₂₀ arylene groups which do not have ring heteroatoms(i.e., C₆₋₂₀ carboarylene groups) include, but are not limited to, thosederived from the compounds discussed above in regard to aryl groups,e.g. phenylene, and also include those derived from aryl groups whichare bonded together, e.g. phenylene-phenylene (diphenylene) andphenylene-phenylene-phenylene (triphenylene).

Alternatively, the ring atoms may include one or more heteroatoms, as in“heteroarylene groups” (e.g., C₅₋₁₀ heteroarylene). A heteroarylenegroup may be unsubstituted or substituted, for instance, as specifiedabove for aryl. Typically a substituted heteroarylene group carries 1, 2or 3 substituents, for instance 1 or 2.

Examples of heteroarylene groups include, but are not limited to, thosederived from the compounds discussed above in regard to heteroarylgroups. Examples of heteroarylene groups include bidentate groupsderived from pyridine, pyrazine, pyrimidine, pyridazine, furan,thiofuran, pyrazole, pyrrole, oxazole, oxadiazole, isoxazole,thiadiazole, thiazole, isothiazole, imidazole and pyrazole.

A perfluoroarylene group is a perfluorinated arylene group.“Perfluorinated” in this context means completely fluorinated such thatthere are no carbon-bonded hydrogen atoms replaceable with fluorine.Typically it is tetrafluorophenylene.

As used herein the term halo is a group selected from —F, —Cl, —Br, and—I.

As used herein the term keto represents a group of formula: ═O

As used herein the term nitro represents a group of formula: —NO₂

As used herein the term cyano represents a group of formula: —CN

As used herein the term hydroxyl represents a group of formula: —OH

As used herein the term thiol represents a group of formula: —SH

As used herein the term sulfonyl represents a group of formula: —S(O)₂R′wherein R′ is a C₁₋₁₀ alkyl group, preferably a C₁₋₆ alkyl group, asdefined previously.

As used herein the term acyl represents a group of formula: —C(═O)R,wherein R is an acyl substituent, for example, a substituted orunsubstituted C₁₋₂₀ alkyl group, a substituted or unsubstituted C₃₋₂₀heterocyclyl group, or a substituted or unsubstituted aryl group.Examples of acyl groups include, but are not limited to, —C(═O)CH₃(acetyl), —C(═O)CH₂CH₃ (propionyl), —C(═O)C(CH₃)₃ (t-butyryl), and—C(═O)Ph (benzoyl, phenone).

As used herein the term acyloxy (or reverse ester) represents a group offormula: —OC(═O)R, wherein R is an acyloxy substituent, for example,substituted or unsubstituted C₁₋₂₀ alkyl group, a substituted orunsubstituted C₃₋₂₀ heterocyclyl group, or a substituted orunsubstituted aryl group, typically a C₁₋₆ alkyl group. Examples ofacyloxy groups include, but are not limited to, —OC(═O)CH₃ (acetoxy),—OC(═O)CH₂CH₃, —OC(═O)C(CH₃)₃, —OC(═O)Ph, and —OC(═O)CH₂Ph.

As used herein the term ester (or carboxylate, carboxylic acid ester oroxycarbonyl) represents a group of formula: —C(═O)OR, wherein R is anester substituent, for example, a substituted or unsubstituted C₁₋₂₀alkyl group, a substituted or unsubstituted C₃₋₂₀ heterocyclyl group, ora substituted or unsubstituted aryl group (typically a phenyl group).Examples of ester groups include, but are not limited to, —C(═O)OCH₃,—C(═O)OCH₂CH₃, —C(═O)OC(CH₃)₃, and —C(═O)OPh.

As used herein the term amino represents a group of formula —NH₂. Theterm C₁-C₁₀ alkylamino represents a group of formula —NHR′ wherein R′ isa C₁₋₁₀ alkyl group, preferably a C₁₋₆ alkyl group, as definedpreviously. The term di(C₁₋₁₀)alkylamino represents a group of formula—NR′R″ wherein R′ and R″ are the same or different and represent C₁₋₁₀alkyl groups, preferably C₁₋₆ alkyl groups, as defined previously. Theterm arylamino represents a group of formula —NHR′ wherein R′ is an arylgroup, preferably a phenyl group, as defined previously. The termdiarylamino represents a group of formula —NR′R″ wherein R′ and R″ arethe same or different and represent aryl groups, preferably phenylgroups, as defined previously. The term arylalkylamino represents agroup of formula —NR′R″ wherein R′ is a C₁₋₁₀ alkyl group, preferably aC₁₋₆ alkyl group, and R″ is an aryl group, preferably a phenyl group.

As used herein the term amido represents a group of formula:—C(═O)NR′R″, wherein R′ and R″ are independently H or aminosubstituents, as defined for di(C₁₋₁₀)alkylamino groups. Examples ofamido groups include, but are not limited to, —C(═O)NH₂, —C(═O)NHCH₃,—C(═O)N(CH₃)₂, —C(═O)NHCH₂CH₃, and —C(═O)N(CH₂CH₃)₂, as well as amidogroups in which R′ and R″, together with the nitrogen atom to which theyare attached, form a heterocyclic structure as in, for example,piperidinocarbonyl, morpholinocarbonyl, thiomorpholinocarbonyl, andpiperazinocarbonyl.

As used herein, the terms “carboxy”, “carboxyl” and “carboxylic acid”each represent a group of the formula: —C(═O)OH, or —COOH. As would beunderstood by the skilled person, a carboxylic acid group (for instance,when employed in the present invention) can exist in protonated anddeprotonated forms (for example, —C(═O)OH and —C(═O)(O⁻), and in saltforms (for example, —C(═O)O⁻X⁺, wherein X⁺ is a monovalent cation).

As used herein the term acylamido represents a group of formula:—NR^(x)C(═O)R^(y), wherein R^(x) is an amide substituent, for example,hydrogen, a C₁₋₂₀ alkyl group, a C₃₋₂₀ heterocyclyl group, an arylgroup, preferably hydrogen or a C₁₋₂₀ alkyl group, and R^(y) is an acylsubstituent, for example, a C₁₋₂₀ alkyl group, a C₃₋₂₀ heterocyclylgroup, or an aryl group, preferably hydrogen or a C₁₋₂₀ alkyl group.Examples of acylamide groups include, but are not limited to,—NHC(═O)CH₃, —NHC(═O)CH₂CH₃, —NHC(═O)Ph, —NHC(═O)C₁₅H₃₁ and—NHC(═O)C₉H₁₉. Thus, a substituted C₁₋₂₀ alkyl group may comprise anacylamido substituent defined by the formula —NHC(═O)—C₁₋₂₀ alkyl, suchas —NHC(═O)C₁₅H₃₁ or —NHC(═O)C₉H₁₉. R^(x) and R^(y) may together form acyclic structure, as in, for example, succinimidyl, maleimidyl, andphthalimidyl:

A C₁₋₁₀ alkylthio group is a said C₁₋₁₀ alkyl group, preferably a C₁₋₆alkyl group, attached to a thio group. An arylthio group is an arylgroup, preferably a phenyl group, attached to a thio group.

A C₁₋₂₀ alkoxy group is a said substituted or unsubstituted C₁₋₂₀ alkylgroup attached to an oxygen atom. A C₁₋₁₀ alkoxy group is a saidsubstituted or unsubstituted C₁₋₁₀ alkyl group attached to an oxygenatom. A C₁₋₆ alkoxy group is a said substituted or unsubstituted C₁₋₆alkyl group attached to an oxygen atom. A C₁₋₄ alkoxy group is asubstituted or unsubstituted C₁₋₄ alkyl group attached to an oxygenatom. Said C₁₋₂₀, C₁₋₁₀, C₁₋₆ and C₁₋₄ alkyl groups are optionallyinterrupted as defined herein. Examples of C₁₋₄ alkoxy groups include,—OMe (methoxy), —OEt (ethoxy), —O(nPr) (n-propoxy), —O(iPr)(isopropoxy), —O(nBu) (n-butoxy), —O(sBu) (sec-butoxy), —O(iBu)(isobutoxy), and —O(tBu) (tert-butoxy). Further examples of C₁₋₂₀ alkoxygroups are —O(Adamantyl), —O—CH₂-Adamantyl and —O—CH₂—CH₂-Adamantyl. Anaryloxy group is a substituted or unsubstituted aryl group, as definedherein, attached to an oxygen atom. An example of an aryloxy group is—OPh (phenoxy).

As used herein, the term “sulfonic acid” represents a group of theformula: —S(═O)₂OH. As would be understood by the skilled person, asulfonic acid group can exist in protonated and deprotonated forms (forexample, —S(═O)₂OH and —S(═O)₂O⁻), and in salt forms (for example,—S(═O)₂O⁻X⁺, wherein X⁺ is a monovalent cation).

As used herein, the term “sulfonamide” represents a group of formula:—S(O)₂NH₂.

The invention provides a functionalised compound of formula (II), asdefined above, which comprises n carbene precursor groups of thefollowing formula:

which are the same or different, wherein n is an integer equal to orgreater than 3, E is a group which is capable of being converted into acarbene reactive intermediate group, x is 1, and R and L are as definedabove.

The term “carbene precursor group”, as used herein, means a latentreactive group which is capable of being converted into a carbenereactive intermediate by a chemical process or by the application ofenergy, wherein the carbene reactive intermediate is capable of furtherreaction. The “application of energy” may for instance involve theapplication of thermal energy (i.e. heating) or irradiation, althoughany suitable source of energy can be used.

An example of a carbene precursor group, E, which is capable of beingconverted into a carbene reactive intermediate, is a diazo group, asfollows:

Thus, E may be a diazo group.

A further example of a carbene precursor group, E, which is capable ofbeing converted into a carbene reactive intermediate, is a hydrazonegroup of formula (1e″):

wherein R¹ is H or —S(O)₂R², wherein R² is an unsubstituted orsubstituted C₁₋₆ alkyl group or an unsubstituted or substituted arylgroup.

Typically, R² is C₁₋₆ alkyl, phenyl or naphthyl, which phenyl ornaphthyl is unsubstituted or substituted with C₁₋₆ alkyl, di(C₁₋₆alkyl)amino, hydroxyl, nitro, cyano or methoxy.

More typically, R² is C₁₋₆ alkyl, phenyl or naphthyl, which phenyl ornaphthyl is unsubstituted or substituted with C₁₋₆ alkyl or di(C₁₋₆alkylamino.

Typically, R¹ is —S(O)₂R² wherein R² is phenyl substituted with C₁₋₆alkyl. More typically, R¹ is —S(O)₂R² wherein R² is phenyl substitutedwith methyl (i.e. tolyl). Thus, in one embodiment, R¹ is a tosyl group.In another embodiment, R¹ is H.

Such hydrazone groups are “carbene precursor groups”, because they arecapable of conversion into carbene reactive intermediates. When R¹ is Hthis conversion may be achieved by oxidation of the hydrazone to adiazomethane followed by the application of energy, typically by heatingor by irradiation. When R¹ is —S(O)₂R² conversion of the Nsulfonylhydrazone group into the carbene reactive intermediate isachieved by treatment with a base followed by the application of energy,typically by heating or by irradiation. Any suitable base may be used,for instance an organic base such as a trialkyl amine (e.g.triethylamine) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).Alternatively an inorganic base may be used, such as an alkali metalhydroxide, e.g. sodium, lithium or potassium hydroxide. Thedecomposition of the sulfonyl hydrazone to the carbene is thought tooccur by elimination of R¹, to form a diazo intermediate group, andsubsequent elimination of dinitrogen to form the reactive carbeneintermediate. Accordingly, E may be a hydrazone group of formula (1e″)as defined above.

Although each of the n carbene precursor groups in the functionalisedcompound of the invention falls within the formula

the groups E which are capable of being converted into carbene reactiveintermediate groups, the linker groups (or single bonds) L, and/or theterminal groups R, may differ from one [R]_(x)-E-L- group to the next inthe functionalised compound. For instance, the functionalised compoundmay comprise a first carbene precursor group of formula [R]_(x)-E-L- anda second carbene precursor group of formula [R]_(x)-E-L-, wherein thegroups E which are capable of being converted into carbene reactiveintermediate groups, the linker groups (or single bonds) L, and/or theterminal groups R are different in the first and second carbeneprecursor groups [R]_(x)-E-L-.

Accordingly, the n carbene precursor groups of the formula:

in the compound of formula (II) are the same or different and areindependently selected from groups of the following formulae (Ia) and(Ie):

wherein R and L are as defined above and, in the group of formula (Ie),R¹ is as defined above.

Typically, however, E is the same group in all of the precursor groupsin the functionalised compound. Similarly, L is typically the same inall of the precursor groups in the functionalised compound. Similarly, Ris typically the same terminal group in all of the precursor groups inthe compound.

The number of reactive intermediate precursor groups in thefunctionalised compound, n, is an integer equal to or greater than 3. Inanother embodiment, n is greater than or equal to 4.

In one embodiment, n is an integer of from 3 to 50 or, for instance,from 4 to 50. More typically n is an integer of from 3 to 20, from 3 to10, from 4 to 20, or from 4 to 10, or an integer of 3, 4 or 5.

In another embodiment, however, n is an integer of from 3 to 500, or forinstance from 4 to 500, and is more typically an integer of from 3 to200, or for instance from 4 to 200, from 3 to 100, from 4 to 100, orfrom 10 to 100, for instance from 10 to 50.

In yet another embodiment, n is an integer equal to or greater than 50,for instance equal to or greater than 100. Thus, n may be an integer offrom 50 to 1,000,000, from 50 to 100,000, from 50 to 10,000, from 50 to5,000, or from 50 to 1,000. More typically, in this embodiment, n is aninteger of from 50 to 1,000.

The functionalised compound of the invention is a compound of formula(II)

wherein n, x, L, R, E and Q are as defined herein.

The carbene precursor groups, E, which are capable of being convertedinto carbene reactive intermediate groups, the linker groups (or singlebonds) L, and the terminal groups R, may differ from one [R]_(x)-E-L-group to the next in the functionalised compound, but are typically thesame.

Thus, each of the [R]_(x)-E-L- groups in the functionalised compound ofthe invention of formula (II), which are the same or different, isindependently selected from a group of formula (Ie) and a group offormula (Ia):

wherein R, L and R¹ are as defined above.

In one embodiment, the [R]_(x)-E-L- groups in the functionalisedcompound of the invention of formula (II) are hydrazone groups offormula (Ie).

Accordingly, in one embodiment, the invention provides a functionalisedcompound which is a hydrazone compound of formula (XXX)

wherein:

n is an integer equal to or greater than 3;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)allylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ allylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²;

R¹ is H or —S(O)₂R², wherein R² is an unsubstituted or substituted C₁₋₆alkyl group or an unsubstituted or substituted aryl group; and

Q is a core moiety, a polymer or a dendrimer;

-   -   with the proviso that when R¹ is H, then:        -   each L is a group of formula (XII); and        -   Q is a core moiety, a dendrimer, or a polymer, which polymer            comprises: a polysaccharide, a protein, a polyester, a            polyether, a polyacrylate, a polymethacrylate, a            polycarbonate, polyetheretherketone (PEEK), a            polyetherimide, a polyimide, a polysulfone, poly(vinyl            chloride), a polysilane, a polysiloxane, a polyurea, a            polyurethane, polylactic acid, polyvinylidene chloride, a            fluoro-polymer, a polyethylene imine, or a salt thereof.

The linker groups L, and the terminal groups R, may differ from onecarbene precursor group to the next in the hydrazone compound, but aretypically the same.

Typically, R² is an unsubstituted or substituted C₁₋₆ alkyl group, anunsubstituted or substituted phenyl group, or an unsubstituted orsubstituted naphthyl group. More typically, R² is C₁₋₆ alkyl, phenyl ornaphthyl, which phenyl or naphthyl is unsubstituted or substituted withC₁₋₆ alkyl, di(C₁₋₆ alkyl)amino, hydroxyl, nitro, cyano or methoxy. R²may for instance be C₁₋₆ alkyl, phenyl or naphthyl, which phenyl ornaphthyl is unsubstituted or substituted with C₁₋₆ alkyl or di(C₁₋₆alkylamino.

In a preferred embodiment, the [R]_(x)-E-L- groups in the functionalisedcompound of the invention of formula (II) are sulfonylhydrazone groups,i.e. groups of formula (Ie) in which R¹ is —S(O)₂R², wherein R² is asdefined above.

The ability to generate a carbene from a sulfonylhydrazone group withoutisolating the diazo group intermediate provides numerous advantages.Such sulfonylhydrazone groups are particularly advantageous because theyare capable of being converted into a carbene reactive intermediategroup, yet they are more stable than the diazo groups of formula (Ia).In particular, they act as a protected precursor to the carbene reactiveintermediate and thereby allow a greater level of control over unwanteddegradation of the functionalized compound of the invention, such as intransport or storage. Of particular significance is the decreasedtoxicity of a sulfonylhydrazone group over a diazo group.Sulfonylhydrazone groups also offer a greater flexibility with regardsto formulation as they are not degraded by carboxylic acids unlike diazogroups such as diazo esters, diazo ketones and alkyl or aryl diazos.

Accordingly, in another embodiment the functionalised compound of theinvention is a sulfonylhydrazone compound of formula (XXXa)

wherein:

n is an integer equal to or greater than 3;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ diaryl(C₁₋₂₀alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²;

R² is an unsubstituted or substituted C₁₋₆ alkyl group or anunsubstituted or substituted aryl group; and

Q is a core moiety, a polymer or a dendrimer.

The linker groups L, and the terminal groups R, may differ from onecarbene precursor group to the next in the sulfonylhydrazone compound,but are typically the same.

Typically, in the functionalised compounds of the invention, R² is anunsubstituted or substituted C₁₋₆ alkyl group, an unsubstituted orsubstituted phenyl group, or an unsubstituted or substituted naphthylgroup. More typically, R² is C₁₋₆ alkyl, phenyl or naphthyl, whichphenyl or naphthyl is unsubstituted or substituted with C₁₋₆ alkyl,di(C₁₋₆ alkyl)amino, hydroxyl, nitro, cyano or methoxy. R² may forinstance be C₁₋₆ alkyl, phenyl or naphthyl, which phenyl or naphthyl isunsubstituted or substituted with C₁₋₆ alkyl or di(C₁₋₆ alkylamino.

In one embodiment, R² is tolyl. Usually, R² is para-tolyl (in which casethe —S(O)₂R² groups are tosyl groups).

In one embodiment, the [R]_(x)-E-L- groups in the functionalisedcompound of the invention of formula (II) are diazo groups of formula(Ia).

Accordingly, in another embodiment, the functionalised compound of theinvention is a diazo-functionalised compound of formula (IIa)

wherein:

n is an integer equal to or greater than 3;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which may be the same or different, is a group of formula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a dendrimer or a polymer, which polymer comprises: apolysaccharide, a protein, a polyester, a polyether, a polyacrylate, apolymethacrylate, a polycarbonate, polyetheretherketone (PEEK), apolyetherimide, a polyimide, a polysulfone, poly(vinyl chloride), apolysilane, a polysiloxane, a polyurea, a polyurethane, polylactic acid,polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or asalt thereof.

The linker groups L, and the terminal groups R, may differ from onecarbene precursor group to the next in the diazo-functionalisedcompound, but are typically the same.

In another embodiment, the [R]_(x)-E-L- groups in the functionalisedcompound of the invention of formula (II) are hydrazone groups offormula (Ie) in which R¹ is H.

Accordingly, in another embodiment, the functionalised compound of theinvention is a hydrazone compound of formula (XXXb)

wherein:

n is an integer equal to or greater than 3;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which may be the same or different, is a group of formula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a dendrimer or a polymer, which polymer comprises: apolysaccharide, a protein, a polyester, a polyether, a polyacrylate, apolymethacrylate, a polycarbonate, polyetheretherketone (PEEK), apolyetherimide, a polyimide, a polysulfone, poly(vinyl chloride), apolysilane, a polysiloxane, a polyurea, a polyurethane, polylactic acid,polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or asalt thereof.

The linker groups L, and the terminal groups R, may differ from onecarbene precursor group to the next in the hydrazone compound, but aretypically the same.

The reactivity of the functionalised compound of the invention and itsderived carbene reactive intermediate can be modified by includingelectron releasing or electron withdrawing groups on the aromatic arylor heteroaryl ring of the terminal group R. In addition, the solubilityof the functionalised compound and its derived carbene reactiveintermediate can be modified by including groups of a givenhydrophilicity or lipophilicity on the aromatic ring. Thus, in thefunctionalised compounds of the invention, each R group is selected fromaryl and heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino,C₁₋₁₀)alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino,arylalkylamino, amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy,aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid,sulfonyl, sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl.

More typically, R is phenyl which is unsubstituted or substituted byone, two, three, four or five groups, which groups are the same ordifferent and are independently selected from C₁₋₂₀ alkyl, C₂₋₂₀alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl.

In the functionalised compounds of the invention, each L, which is thesame or different, is a single bond or a group of formula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A².

Typically, A¹ is an unsubstituted or substituted arylene group. Moretypically, A¹ is an unsubstituted or substituted phenylene group, evenmore typically an unsubstituted phenylene group.

Usually, A² is an unsubstituted or substituted group selected from C₁₋₂₀alkylene, C₁₋₂₀ perfluoroalkylene, *—C₁₋₂₀ alkylene-(O—C₁₋₂₀alkylene-)_(m) wherein m is 1 to 20, *—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀perfluoroalkylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl. More typically, A² is C₁₋₁₀ alkylene or *—C₁₋₆alkylene-(O—C₂₋₄ alkylene-)_(m) wherein m is 1 to 20 and wherein * isthe point of attachment of A² to A¹.

In one embodiment, A¹ is a phenylene group, typically an unsubstitutedphenylene group, and A² is C₁₋₁₀ alkylene or *—C₁₋₆ alkylene-(O—C₂₋₄alkylene-)_(m) wherein m is 1 to 20 and wherein * is the point ofattachment of A² to A¹.

Typically, A³ is a single bond, O, C(O), *—OC(O) or an unsubstituted orsubstituted group selected from *—Z²-arylene, *—Z²-heteroarylene,arylene, heteroarylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*-arylene-O and *-heteroarylene-O, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A².

More typically, A³ is a single bond, O, C(O), *—OC(O) or anunsubstituted or substituted group selected from *—O-arylene,*—O-heteroarylene, *—O-arylene-O and *—O-heteroarylene-O wherein * isthe point of attachment of A³ to A². Even more typically, A³ is a singlebond, O, or an unsubstituted or substituted group selected from*—O-arylene, *—O-heteroarylene, *—O-arylene-O and *—O-heteroarylene-Owherein * is the point of attachment of A³ to A². Even more typically,A³ is a single bond, O, or an unsubstituted or substituted groupselected from *—O-heteroarylene and *—O-heteroarylene-O wherein * is thepoint of attachment of A³ to A².

In one embodiment, each L within the functionalised compound of theinvention is independently selected from the following groups:

wherein * is the point of attachment of L to the carbon atom bonded toR, and wherein X^(L) is halo, hydroxyl, C₁₋₁₀ alkoxy, C₁₋₂₀ alkyl, C₂₋₂₀alkenyl, C₂₋₂₀ alkynyl, aryl, aralkyl, cyano, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,acylamido, C₁₋₂₀ haloalkyl, ester, acyl, acyloxy, aryloxy, nitro,carboxy, sulfonic acid, sulfonyl, sulphonamide, thiol, C₁₋₁₀ alkylthioor arylthio.

Typically, X^(L) is halo or hydroxyl. More typically, X^(L) is halo, forinstance chloro.

In some embodiments, wherein the functionalised compound of theinvention comprises hydrazone groups of formula (Ie) in which R¹ is—S(O)₂R² (i.e. sulfonylhydrazone groups), L may be a single bond. Insuch embodiments, the carbon atoms of the carbene precursor groups(which carbon atoms are bonded to R) are bonded directly to Q.

Q is a core moiety, a polymer or a dendrimer. The core moiety, polymeror dendrimer is functionalised with said n carbene precursor groups[R]_(x)-E-L- in said compound of formula (II). As is shown in formula(II), each of the n reactive carbene precursor groups is bonded to thecore moiety, polymer or dendrimer, Q, via the group L of the carbeneprecursor group, which may be a linking group or a single bond. When Lis a group of formula (XII) as defined above, each of the n reactiveintermediate precursor groups is typically bonded to the core moiety,polymer or dendrimer, Q, via group A³ of said group of formula (XII).

As is described in further detail below, the functionalised compounds offormula (II) may be synthesised by coupling the carbene precursor groups(or carbonyl precursors thereto) to a core moiety, polymer or dendrimerQ′ by reaction between a functional group on the linker moiety of thecarbene precursor group (or on the carbonyl precursor) with functionalgroups, -A⁴-X² on Q′. Thus, the core moiety, polymer or dendrimer Q ofthe compound of formula (II) is typically attached to the groups L ofthe n carbene precursor groups via n linker groups of formula A⁴.

Accordingly, Q in the functionalised compounds of the invention istypically a core moiety, a polymer or a dendrimer which comprises nlinker groups of formula A⁴, each of which is attached to a group L,wherein n is an integer equal to or greater than 3. Each individual A⁴is the same as or different from the others and is independentlyselected from a single bond, —Z³-arylene-*, —Z³-heteroarylene-*,—Z³—C₁₋₂₀ alkylene-*, arylene, heteroarylene, C₁₋₂₀ alkylene,—Z³-arylene-O—*, —Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ alkylene-O—*,arylene-O—*, heteroarylene-O—*, C₁₋₂₀ alkylene-O—*, —C(O)—*, S(O)₂,—OC(O)—*, —N(R″)C(O)—*, O, S, N(R″), —C(O)O—*, —C(O)N(R″)—*, —S(O)₂O—*,C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, —Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀alkynylene-*, wherein Z³ is selected from O, S, N(R″), C(O), S(O),S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ isindependently selected from H, C₁₋₆ alkyl and aryl, and wherein * is thepoint of attachment of A⁴ to L.

In one embodiment, each A⁴ is independently selected from O,arylene-O—*, heteroarylene-O—*, C₁₋₂₀ alkylene-O—*, —Z³-arylene-O—*,—Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ alkylene-O—*, wherein Z³ is selectedfrom O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) andN(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆ alkyland aryl, wherein * is the point of attachment of A⁴ to L. Moretypically, in this embodiment, A⁴ is O.

In another embodiment, each A⁴ is independently selected from a singlebond, —Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀ alkylene-*, arylene,heteroarylene, C₁₋₂₀ alkylene, —C(O)—, S(O)₂, —OC(O)—*, —N(R″)C(O)—*,C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, —Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀allynylene-*, wherein Z³ is selected from O, S, N(R″), C(O), S(O),S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ isindependently selected from H, C₁₋₆ alkyl and aryl, and wherein * is thepoint of attachment of A⁴ to L.

In a further embodiment, A⁴ is —C(O)—.

In another embodiment, A⁴ is —Z³-heteroarylene-* wherein * is the pointof attachment of A⁴ to L. Typically, Z³ is O. Typically, in thisembodiment, A⁴ is a group of formula (XIX)

wherein * is the point of attachment to L and wherein X^(L) is halo,hydroxyl, C₁₋₁₀ alkoxy, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, aryl,aralkyl, cyano, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, acylamido, C₁₋₂₀ haloalkyl, ester,acyl, acyloxy, aryloxy, nitro, carboxy, sulfonic acid, sulfonyl,sulphonamide, thiol, C₁₋₁₀ alkylthio or arylthio.

Typically, X^(L) is halo or hydroxyl. More typically, X^(L) is halo, forinstance chloro.

In one embodiment, Q is a dendrimer, which dendrimer comprises n surfacegroups which are linker groups of formula A⁴ as defined above. The nlinker groups A⁴ are the same as or different from one another andbonded to the n L groups of the n carbene precursor groups [R]_(x)-E-L-in said compound of formula (II). Any suitable dendrimer structure maybe employed. When Q is a dendrimer, n is typically an integer of from 3to 500, or from 4 to 500, and is more typically an integer of from 3 to200, or from 4 to 200, from 3 to 100, or from 4 to 100, or from 10 to100, for instance from 10 to 50.

Any suitable dendrimer may be used. PAMAM dendrimers are suitable, forinstance.

When Q comprises a polymer, the polymer may be a linear polymer, abranched polymer or a hyperbranched polymer. The polymer may forinstance be a homopolymer or a copolymer. The co-polymer may be ater-polymer or any other multiple combination polymer. Suitablecopolymers include polymethylmethacrylate-co-poly-2-dimethylamino ethylmethacrylate, for instance.

Also covered are different polymer architectures, including but notlimited to branched polymers; block copolymers, for instance, SBS rubber(Kraton), or EO-PO-EO (Pluronic); star polymers (Tetronic); orhyperbranched polymers (PEI).

Polymers of different molecular weight ranges are also covered, fromsmall macromers with a repeat unit length of a dimer, to polymers with amolecular weight of millions. The degree of polymerisation, Dp, of thepolymer (i.e. the polymer molecular weight divided by the molecularweight of the repeat unit) may be from 2 to 100,000,000.

Typically, the polymer employed is either soluble or dispersable.

When Q comprises a polymer, the polymer may be a homo-polymer or acopolymer.

In one embodiment, when Q comprises a polymer, the polymer is selectedfrom any of the polymers listed in the following paragraph and theircopolymers. Thus, the polymer may be a homopolymer comprising any of thefollowing polymers, or a copolymer which comprises the monomeric unitsof any one or more of the following polymers:

Condensation polymers and Addition polymers. Polysaccharides, includingbut not limited to chitin, guar gums, gum arabic, galactomannans, forinstance locust bean gum (LBG). Proteins, including but not limited toKeratin. Polyesters, including but not limited to Nylon, polyethyleneterephthalate (PET) and polyoxyethylene terephthalate (POET).Polyethers, including but not limited to polypropylene glycol (PPG),polyethylene gloycol (PEG), Polyethylene oxide (PEO). Polyolefins,including but not limited to polyethylene (PE), polypropylene (PP), andco-polymers thereof. Polyolefin co-polymers. Polyacrylates andpolymethacrylates, including but not limited to polyacric acid (PAA)polymethacrylic acid (PMAA), Poly2-dimethylamino methacrylate (PDMAEMA),Poly-2-hydroxyethyl methacylate (PHEMA), acrylonitrile. Polystyrene.Thermoplatic elastomers, including but not limited to, Polybutadiene,Polyisoprene, SBS rubber and SIS rubber. Polycarbonates.Polyetheretherketone (PEEK). Polyetherimides. Polyimides. Polysulfones.Poly vinyl chloride (PVC). Polysilanes. Polysiloxanes. Polyureas.Polyurethanes. Polylactic acid. Polyvinylidene chloride. Polyethyleneimines.

When Q comprises a polymer, the polymer may be a salt of any of thepolymers described herein.

In some embodiments, when Q comprises a polymer, the polymer comprises apolysaccharide, a protein, a polyester, a polyether, a polyacrylate, apolymethacrylate, a polycarbonate, polyetheretherketone (PEEK), apolyetherimide, a polyimide, a polysulfone, poly(vinyl chloride), apolysilane, a polysiloxane, a polyurea, a polyurethane, polylactic acid,polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or asalt thereof.

Typically, the polymer is one that has a functionality -A⁴-X² as definedherein, for instance an OH, NH, SH or aryl (typically phenyl)functionality that allows single step transformation to introduce thereactive intermediate precursor groups of formula (I) onto the polymer.

Alternatively, however, any polymer can be modified to include thereactive intermediate precursor group using a two-step process. In sucha process, an -A⁴-X² functionality, for instance an —OH, NH, SH or aryl(typically phenyl) functionality is first reacted onto the desiredpolymer. Subsequently, that -A⁴-X² functionality, which has beennewly-introduced on the polymer, is coupled with a further compound,which comprises the reactive intermediate precursor group of formula(I), to introduce that reactive intermediate precursor group onto thepolymer.

Thus, when Q comprises a polymer, for instance any of the polymersdefined above, the polymer typically comprises n linker groups offormula A⁴ which are the same or different and are as defined above,each of which is attached to a group L of a reactive intermediateprecursor group of formula (I), wherein n is an integer equal to orgreater than 2.

In one embodiment, A⁴ is O or —Z³-heteroarylene-* wherein * is the pointof attachment of A⁴ to L. Typically, Z³ is O. More typically, in thisembodiment, A⁴ is O or a group of formula (XIX) as defined above.

In one embodiment, Q comprises a polysaccharide, a polyester orpolystyrene.

In one embodiment, when Q comprises a polysaccharide, the polysaccharideis a chitin, guar gum, gum arabic, or a galactomannan, for instancelocust bean gum (LBG).

In one embodiment, when Q comprises a polyester, the polyester is Nylon,polyethylene terephthalate (PET) or polyoxyethylene terephthalate(POET).

As mentioned above, in some embodiments of the functionalised compoundof the invention, L may be a single bond.

Typically, when L is a single bond, Q comprises at least n aryl orheteroaryl rings, wherein each L which is single bond is attacheddirectly to a said aryl or heteroaryl ring of Q. The single bond, L,thereby bonds the aryl or heteroaryl ring directly to the carbon atom ofthe carbene precursor group (i.e. the carbon atom that is also bonded toR in the functionalised compound of the invention). In this embodiment Qis a core moiety, polymer or dendrimer that comprises said n aryl orheteroaryl rings. Typically, said aryl or heteroaryl rings are arylrings. Usually, said aryl rings are phenyl rings. Examples of polymersthat comprise aryl rings include, for instance, polystyrene, a copolymercomprising polystyrene, a thermoplastic elastomer, polyisoprene, acopolymer comprising polyisoprene, SBS rubber, SIS rubber orpoly(styrene)-poly(ethylene/butylene)-poly(styrene) (SEBS).

More typically, when L is a single bond, Q is a polymer which comprisesat least n aryl or heteroaryl rings, wherein each L which is single bondis attached directly to a said aryl or heteroaryl ring, thereby bondingthe aryl or heteroaryl ring directly to the carbon atom which is bondedto R. Typically, said aryl or heteroaryl rings are aryl rings.Typically, said aryl rings are phenyl rings.

Thus, in some embodiments of the functionalised compound of theinvention, L is a single bond and Q is a polymer which comprises atleast n aryl or heteroaryl rings, wherein each L which is single bond isattached directly to a said aryl or heteroaryl ring, thereby bonding thearyl or heteroaryl ring directly to the carbon atom which is bonded toR. Typically, said aryl or heteroaryl rings are aryl rings. Typically,said aryl rings are phenyl rings. Usually, in such embodiments, Qcomprises polystyrene, a copolymer comprising polystyrene, athermoplastic elastomer, polyisoprene, a copolymer comprisingpolyisoprene, SBS rubber, SIS rubber orpoly(styrene)-poly(ethylene/butylene)-poly(styrene) (SEBS).

Typically, when Q comprises a polymer, n is an integer equal to orgreater than 50, for instance equal to or greater than 100. Thus, n maybe an integer of from 50 to 1,000,000, from 50 to 100,000, from 50 to10,000, from 50 to 5,000, or from 50 to 1,000. More typically, in thisembodiment, n is an integer of from 50 to 1,000.

In one embodiment, Q is a core moiety which is a straight-chained orbranched, saturated or unsaturated C₁₋₂₀ hydrocarbon moiety; an arylring; a heteroaryl ring; a C₅₋₁₀ carbocyclic ring; a C₅₋₁₀ heterocyclicring; or a fused bi-, tri- or tetracyclic ring system wherein each ringof said fused bi-, tri- or tetracyclic ring system is independentlyselected from an aryl ring, a heteroaryl ring, a C₅₋₁₀ carbocyclic ringand a C₅₋₁₀ heterocyclic ring;

wherein said hydrocarbon moiety, aryl ring, heteroaryl ring, carbocyclicring, heterocyclic ring or fused bi-, tri- or tetracyclic ring system issubstituted with said n linker groups, A⁴, and is otherwiseunsubstituted or substituted, wherein each A⁴ is the same or differentand is as defined hereinbefore and wherein each A⁴ is attached to agroup L.

Typically, when Q is a core moiety, n is an integer of from 3 to 50, orfrom 4 to 50, more typically an integer of from 3 to 20, or from 4 to20, or from 3 to 10, or from 4 to 10, or an integer of 3, 4 or 5.

Typically, n is an integer of from 3 to 10 and Q is a core moiety offormula (XIV):

wherein each A⁴ is the same or different and is as defined above, andwherein A is an aryl ring, a heteroaryl ring, a C₅₋₁₀ carbocyclic ring,a C₅₋₁₀ heterocyclic ring, or a fused bi-, tri- or tetracyclic ringsystem wherein each ring of said fused bi-, tri- or tetracyclic ringsystem is independently selected from an aryl ring, a heteroaryl ring, aC₅₋₁₀ carbocyclic ring and a C₅₋₁₀ heterocyclic ring.

Typically, in this embodiment, A is an aryl ring or a heteroaryl ring.Typically, n is an integer of from 3 to 6.

In another embodiment, n is an integer of from 3 to 10 and Q is a coremoiety of formula (XVI):

wherein each A⁴ is the same or different and is as defined above, andwherein A^(HC) is straight-chained or branched, saturated or unsaturatedC₁₋₂₀ hydrocarbon moiety which is otherwise unsubstituted orsubstituted.

Typically, in this embodiment, n is an integer of from 3 to 6.

Typically, the C₁₋₂₀ hydrocarbon moiety is a straight-chained orbranched C₁₋₁₀ hydrocarbon moiety which is substituted with said n A⁴linkers and is otherwise unsubstituted or substituted. For instance, itmay be a methane, ethane, propane, butane, pentane, hexane, heptane,octane, nonane or decane moiety which is substituted with said n A⁴linkers and otherwise unsubstituted or substituted. The hydrocarbon maybe straight-chained or branched. Thus, for instance, a propanehydrocarbon moiety may be i-propane or n-propane and a butane moiety maybe t-butane, s-butane, i-butane or n-butane.

In one embodiment, n is 3.

In one embodiment, n is 3 and Q is a core moiety of formula (XIVa)

wherein each A⁴ is the same or different and is as defined hereinbeforeand wherein A is an aryl or heteroaryl ring. Typically, in thisembodiment, each A⁴ is independently selected from C(O), O, arylene-O—*,heteroarylene-O—*, C₁₋₂₀ alkylene-O—*, —Z³-arylene-O—*,—Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ alkylene-O—*, wherein Z³ is selectedfrom O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) andN(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆ alkyland aryl, wherein * is the point of attachment of A⁴ to L. Moretypically, in this embodiment, each A⁴ is independently selected fromC(O) and O. Even more typically, in this embodiment, A⁴ is C(O).

In another embodiment, n is 3 and Q is a core moiety of formula (XVIa)

wherein A⁴ is the same or different and is as defined hereinbefore andwherein q, m and p are the same or different and are independentlyselected from 0 and an integer of 1 to 20. Typically, in thisembodiment, each A⁴ is independently selected from C(O), O, arylene-O—*,heteroarylene-O—*, C₁₋₂₀ alkylene-O—*, —Z³-arylene-O—*,—Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ alkylene-O—*, wherein Z³ is selectedfrom O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) andN(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆ alkyland aryl, wherein * is the point of attachment of A⁴ to L. Moretypically, in this embodiment, each A⁴ is independently selected fromC(O) and O. Even more typically, in this embodiment, A⁴ is O.

In another embodiment, n is 3 and Q is any one of the following coremoieties:

In one embodiment of the functionalised compound of the invention, L isa group of formula (XII) as defined above, in which A³ is a single bondor an unsubstituted or substituted group selected from *—Z²-arylene,*—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene, heteroarylene, C₁₋₂₀alkylene, C(O), S(O)₂, *—OC(O) and *—N(R″)C(O), wherein Z² is selectedfrom O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) andN(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆ alkyland aryl, and wherein * is the point of attachment of A³ to A².

Typically, in this embodiment, A³ is a single bond.

Alternatively, A³ may be an unsubstituted or substituted group selectedfrom *—O-arylene and *—O-heteroarylene wherein * is the point ofattachment of A³ to A². For instance, A³ may be a group of formula(XVII)

wherein * is the point of attachment of A³ to A², and wherein X^(L) ishalo, hydroxyl, C₁₋₁₀ alkoxy, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl,aryl, aralkyl, cyano, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, acylamido, C₁₋₂₀haloalkyl, ester, acyl, acyloxy, aryloxy, nitro, carboxy, sulfonic acid,sulfonyl, sulphonamide, thiol, C₁₋₁₀ alkylthio or arylthio.

Typically, X^(L) is halo or hydroxyl. More typically, X^(L) is halo, forinstance chloro.

Typically, when A³ is an unsubstituted or substituted group selectedfrom *—O-arylene and *—O-heteroarylene, A¹ is unsubstituted orsubstituted phenylene and A² is an unsubstituted or substituted groupselected from C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, *—C₁₋₂₀alkylene-(O—C₁₋₂₀ alkylene-)_(m), wherein m is 1 to 20, *—Z¹—C₁₋₂₀alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀alkylene-)_(m) wherein m is 1 to 20, wherein Z¹ is selected from O, S,C(O), S(O), S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O),wherein * is the point of attachment of A² to A¹, wherein each of saidC₁₋₂₀ alkylene and C₁₋₂₀ perfluoroalkylene groups is optionallyinterrupted by N(R″), O, S or arylene, and wherein each R″ isindependently selected from H, C₁₋₆ alkyl and aryl. More typically, inthis embodiment, A¹ is unsubstituted or substituted phenylene and A² isC₁₋₁₀ alkylene or *—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is1 to 20 and wherein * is the point of attachment of A² to A¹. Even moretypically A² is *—C₁₋₆ alkylene-(O—C₂₋₄ alkylene-)_(m) wherein m is 1 to20 and wherein * is the point of attachment of A² to A¹. Usually, inthese embodiments, A³ is a group of formula (XVII)

wherein * is the point of attachment of A³ to A² and wherein X^(L) is asdefined above. Thus, L may for instance be the following group:

wherein * is the point of attachment of L to the carbon atom bonded to Rand wherein X^(L) is as defined above.

When A³ is a single bond, A¹ is typically unsubstituted or substitutedphenylene and A² is typically unsubstituted or substituted C₁₋₂₀alkylene, for instance unsubstituted or substituted C₁₋₁₀ alkylene,unsubstituted or substituted C₁₋₄ alkylene or CH₂. Thus, L may forinstance be the following group:

wherein * is the point of attachment of L to the carbon atom bonded toR.

In another embodiment, when A³ is a single bond, A¹ and A² are alsosingle bonds and therefore L itself is a single bond. Typically, in thisembodiment, each L is attached to a phenyl group of Q. Typically, inthis embodiment, Q is a core moiety, polymer or dendrimer bearing phenylgroups, more typically a polymer bearing phenyl groups, for instancepolystyrene.

Typically, when L is a group of formula (XII) as defined above, in whichA³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, C(O), S(O)₂, *—OC(O) and *—N(R″)C(O), asdefined above, or in which A³ is as further defined in the precedingparagraphs, Q is a core moiety, polymer or dendrimer comprising n linkeratoms which are oxygen atoms, wherein each of said oxygen atoms isattached to a group L.

Typically, in this embodiment, Q is a polysaccharide. For instance Q maybe chitin, a guar gum, gum arabic or a galactomannan, for instancelocust bean gum (LBG). Such polysaccharides bear terminal OH groupswhich can be converted into said n linker atoms which are oxygen atoms.

Alternatively Q may be a core moiety of formula (XIV) or formula (XVI):

wherein n is an integer of 3 to 10, wherein A and A^(HC) are as definedabove, and wherein each A⁴, which is the same or different, isindependently selected from O, arylene-O—*, heteroarylene-O—*, C₁₋₂₀alkylene-O—*, —Z³-arylene-O—*, —Z³-heteroarylene-O—*, —Z³—C₁₋₂₀alkylene-O—*, wherein Z³ is selected from O, S, N(R″), C(O), S(O),S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ isindependently selected from H, C₁₋₆ alkyl and aryl, wherein * is thepoint of attachment of A⁴ to L.

Alternatively Q may be a core moiety of formula (XIVa) or formula (XVIa)

wherein

A is an aryl or heteroaryl ring;

q, m and p are the same or different and are independently selected from0 and an integer of 1 to 20; and

each A⁴, which is the same or different, is independently selected fromO, arylene-O—*, heteroarylene-O—*, C₁₋₂₀ alkylene-O—*, —Z³-arylene-O—*,—Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ allylene-O—*, wherein Z³ is selectedfrom O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) andN(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆ alkyland aryl, wherein * is the point of attachment of A⁴ to L.

Q may for instance be any one of the following core moieties:

In another embodiment of the functionalised compound of the invention, Lis a group of formula (XII) as defined above, in which A³ is O, S,N(R″), *—C(O)O, *—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀alkynylene, *—Z²—C₁₋₂₀ alkenylene or *—Z²—C₁₋₂₀ alkynylene, wherein Z²is selected from O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″)and N(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl, and wherein * is the point of attachment of A³ to A².Typically, in this embodiment, A³ is O. Typically, in this embodiment,A¹ is unsubstituted or substituted phenylene. A² is typically any A²group as defined hereinbefore. However, A² is more typically C₁₋₂₀alkylene. Typically, therefore A¹ is unsubstituted or substitutedphenylene, A² is C₁₋₂₀ alkylene and A³ is O. Thus, L may be thefollowing group

wherein * is the point of attachment of L to the carbon atom bonded toR.

Typically, in the embodiments defined in the preceding paragraph, Q is acore moiety, polymer or dendrimer which bears n linker groups, each ofwhich is attached to a group L, which linker groups are of formula (XIX)

wherein * is the point of attachment to L, and wherein X^(L) is halo,hydroxyl, C₁₋₁₀ alkoxy, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, aryl,aralkyl, cyano, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino,diarylamino, arylalkylamino, amido, acylamido, C₁₋₂₀ haloalkyl, ester,acyl, acyloxy, aryloxy, nitro, carboxy, sulfonic acid, sulfonyl,sulphonamide, thiol, C₁₋₁₀ alkylthio or arylthio. Typically, X^(L) ishalo or hydroxyl. More typically, X^(L) is halo, for instance chloro.Thus, Q may be a polysaccharide or a polyester which bears said n linkergroups of formula (XIX). Typically, Q is a polyester which bears said nlinker groups. The polyester may for instance be Nylon, polyethyleneterephthalate (PET) or polyoxyethylene terephthalate (POET).

Alternatively Q may be a core moiety of formula (XIV) or formula (XVI):

wherein n is an integer of 3 to 10, wherein A and A^(HC) are as definedabove, and wherein each A⁴, which is the same or different, is selectedfrom a single bond, —Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀alkylene-*, arylene, heteroarylene, C₁₋₂₀ alkylene, —C(O)—*, S(O)₂,—OC(O)—*, —N(R″)C(O)—*, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, —Z³—C₁₋₂₀alkenylene-* and —Z³—C₁₋₂₀ alkynylene-*, wherein Z³ is selected from O,S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O),wherein each R″ is independently selected from H, C₁₋₆ alkyl and aryl,and wherein * is the point of attachment of A⁴ to L.

Alternatively, Q may be a core moiety of formula (XIV) or formula (XVI)

wherein

A is an aryl or heteroaryl ring;

q, m and p are the same or different and are independently selected from0 and an integer of 1 to 20; and

each A⁴, which is the same or different, is selected from a single bond,—Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀ alkylene-*, arylene,heteroarylene, C₁₋₂₀ alkylene, —C(O)—*, S(O)₂, —OC(O)—*, —N(R″)C(O)—*,C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, —Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀alkynylene-*, wherein Z³ is selected from O, S, N(R″), C(O), S(O),S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ isindependently selected from H, C₁₋₆ alkyl and aryl, and wherein * is thepoint of attachment of A⁴ to L.

In one embodiment, A⁴ is C(O). Thus, Q may be the following core moiety:

In one embodiment, the functionalised compound is of formula (XX),formula (XXa), or formula (XXb)

wherein n, Q and X^(L) are as defined hereinbefore and R³ is C₁₋₂₀alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl,C₁₋₂₀ perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino,C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino,arylalkylamino, amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy,aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid,sulfonyl, sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl or triarylsilyl. More typically, R³ is H orNO₂. Even more typically, R³ is NO₂. Typically, X^(L) is halo orhydroxyl. More typically, X^(L) is halo, for instance chloro. Typically,Q comprises a polymer and n is an integer equal to or greater than 50.Typically, the polymer is a polysaccharide, for instance agalactomannan, e.g. locust bean gum. Alternatively, the polymer may be apolyester, for instance nylon, polyethylene terephthalate (PET) orpolyoxyethylene terephthalate (POET).

Typically, the functionalised compound is of formula (XXa).

In another embodiment, the functionalised compound is of formula (XXI),formula (XXIa), or formula (XXIb)

wherein n, Q, R³ and X^(L) are as defined hereinbefore. Typically, R³ isH or NO₂. Even more typically, R³ is NO₂. Typically, X^(L) is halo orhydroxyl. More typically, X^(L) is halo, for instance chloro. Typically,Q comprises a polymer and n is an integer equal to or greater than 50.Typically, the polymer is a polysaccharide, for instance agalactomannan, e.g. locust bean gum. Alternatively, the polymer may be apolyester, for instance nylon, polyethylene terephthalate (PET) orpolyoxyethylene terephthalate (POET).

Typically, the functionalised compound is of formula (XXIa).

In another embodiment, the functionalised compound is of formula (XXII),(XXIIa) or (XXIIb)

wherein n, Q and R³ are as defined hereinbefore. Typically, R³ is H orNO₂. In one embodiment Q comprises a polymer and n is an integer equalto or greater than 50. The polymer may for instance be a polysaccharide,for instance a galactomannan, e.g. locust bean gum. Alternatively Q maybe a polyester which bears n linker groups of formula (XIX) as definedhereinbefore. In another embodiment, Q is a core moiety as definedhereinbefore. Typically, when Q is a core moiety n is an integer of from3 to 50, or from 3 to 10. More typically, when Q is a core moiety n is3. Q may for instance be the following core moiety, wherein n is 3:

In another embodiment, the functionalised compound is of formula(XXIII), (XXIIIy) or (XXIIIz)

wherein r is an integer of from 1 to 4 and each r is the same ordifferent, and n, Q and R³ are as defined hereinbefore. Typically, R³ isH or NO₂. In one embodiment Q comprises a polymer and n is an integerequal to or greater than 50. The polymer may for instance be apolysaccharide, for instance a galactomannan, e.g. locust bean gum. Inanother embodiment, Q is a core moiety as defined hereinbefore.Typically, when Q is a core moiety n is an integer of from 3 to 50. Moretypically, when Q is a core moiety n is an integer of from 3 to 10. Moretypically, when Q is a core moiety n is 3. Q may for instance be any oneof the following core moieties, wherein n is 3:

In another embodiment, the functionalised compound is a compound offormula (XXIV) or (XXV)

wherein n is an integer equal to or greater than 50 and wherein X^(L) ishalo, hydroxyl, C₁₋₁₀ alkoxy, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl,aryl, aralkyl, cyano, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, acylamido, C₁₋₂₀haloalkyl, ester, acyl, acyloxy, aryloxy, nitro, carboxy, sulfonic acid,sulfonyl, sulphonamide, thiol, C₁₋₁₀ allylthio or arylthio. Typically,X^(L) is halo or hydroxyl. More typically, X^(L) is halo, for instancechloro.

In another embodiment, the functionalised compound is a compound offormula (XXIVa) or (XXVa)

wherein n is an integer equal to or greater than 50 and wherein X^(L) ishalo, hydroxyl, C₁₋₁₀ alkoxy, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl,aryl, aralkyl, cyano, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, acylamido, C₁₋₂₀haloalkyl, ester, acyl, acyloxy, aryloxy, nitro, carboxy, sulfonic acid,sulfonyl, sulphonamide, thiol, C₁₋₁₀ alkylthio or arylthio. Typically,X^(L) is halo or hydroxyl. More typically, X^(L) is halo, for instancechloro.

In another embodiment, the functionalised compound is a compound offormula (XXVII), (XXVIIa) or (XXVIII)

In another embodiment, the functionalised compound is a compound offormula (XXVIIb) or (XXVIIc)

wherein R¹ is H or tosyl.

In another embodiment, the functionalised compound is a compound offormula (XXVIb)

wherein n is an integer equal to or greater than 50, R is as definedhereinbefore, R² is as defined hereinbefore, and Q is polystyrene or acopolymer comprising styrene monomer units (a styrene copolymer). Eachsulfonylhydrazone group in the compound of formula (XXVIb) is typicallybonded to a phenyl group of said polystyrene or said copolymercomprising polystyrene.

Typically, the compound is of formula (XXVIc)

wherein n is an integer equal to or greater than 50 and Q is polystyreneor a copolymer comprising styrene monomer units (a styrene copolymer).Each sulfonylhydrazone group in the compound of formula (XXVIc) istypically bonded to a phenyl group of said polystyrene or said copolymercomprising polystyrene. The copolymer comprising styrene monomer unitsmay for instance be poly(styrene)-poly(ethylene/butylene)-poly(styrene)(SEBS).

The multiple reactive intermediate precursor groups of thefunctionalised compounds of the invention can be readily converted intocarbene reactive intermediate groups, which can in turn react with andbond to a wide variety of substrates, including individual molecules andbulk materials.

The carbene reactive intermediate groups are typically generated by athermal process, but can be generated chemically or by irradiation.Typically, the carbene reactive intermediate groups are generated byheating. The functionalised compounds of the invention are usuallyheated to a temperature of from about 100° C. to about 180° C., moretypically from about 110° C. to 160° C., in order to generate saidcarbene reactive intermediate groups. The heat might be applied to thefunctionalised compound externally, but may also be as a result ofanother process, for example, extrusion.

Accordingly, the functionalised compound of the invention, as definedherein, can be used as an agent to form 3-dimensional networks. Sincethe functionalised compounds of the invention bear at least 3 reactiveintermediate precursor groups which can be converted into reactiveintermediate groups, one molecule of the functionalised compound canreact with three or more sites in three dimensions. Therefore, amolecule of the compound can form a network within a single compound, orbetween two or more different compounds, e.g. compounds A and B. Thefunctionalised compound can also react with itself intermolecularly,i.e. with other molecules of the functionalised compound. Thus, a bulksample of the functionalised compound can react both with itself andwith any other material or materials with which it is brought intocontact, to form a covalent network that bonds the materials together.

For instance, the chemical agent could be formulated with a coatingcomprising one or more materials and the reactive intermediate precursorgroups of the functionalised compound may then be converted intoreactive intermediate groups, thereby causing the functionalisedcompound to react with itself intermolecularly and to react with thecomponents of the formulation. Such coatings can contain materials,monomers or polymers in any suitable physical form, for instance in theform of a solution (water on solvent based), a hot melt or a suspensionof materials.

For instance, a bulk layer of a functionalised compound of the inventionmay be applied between two substrates, C and D, and the reactiveintermediate precursor groups of the functionalised compound may then beconverted into reactive intermediate groups, thereby causing thefunctionalised compound to react with itself intermolecularly and toreact with the surfaces of the two substrates, thereby forming a networkbetween E and F, bonding the two substrates together. Such substratesmay be in any suitable physical form, for instance in the form of asolution or suspension of the substrate, or in the form of a solid film,layer, sheet or board. Alternatively, the substrates may be in powderform, or in the form of pellets, beads, particles, nanoparticles ormicroparticles. The pellets, beads or particles may be macroscopicparticles, i.e. visible to the naked eye, or microscopic particles.Thus, the particles could be microparticles or nanoparticles.

Accordingly, the invention provides the use of a functionalised compoundof the invention, as defined herein, as an agent for producing achemically-bound three-dimensional network on or within a substrate.

Further provided is the use of a functionalised compound of theinvention, as defined herein, as a cross linking agent.

Substrate particles, for instance, beads, microparticles, nanoparticles,encapsulates and fluorescent particles, can be cross linked onto, orincorporated on or within a three-dimensional network formed by, thefunctionalised compounds of the invention. The compounds of theinvention can thereby act as carriers or delivery vehicles for thesubstrate particles, to facilitate delivery of the particles to adesired location. Such carrier compounds can be produced by convertingthe reactive intermediate precursor functionalities of a functionalisedcompound of the invention into carbene reactive intermediates in thepresence of such substrate particles. The carbene reactive intermediategroups then react with the particles to couple the microparticles to thecompound.

Accordingly, the invention provides a process for producing a treatedparticle, which process comprises:

(a) contacting a functionalised compound of the invention as definedherein with a substrate particle; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that a carbene reactive intermediate group reactswith the substrate particle to attach the particle to the compound,thereby yielding said treated particle.

The resulting treated particle may act as a carrier or a deliveryvehicle. Accordingly, the invention provides a process for producing aparticle-delivery compound, which process comprises:

(a) contacting a functionalised compound of the invention as definedherein with a substrate particle; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that a carbene reactive intermediate group reactswith the substrate particle to attach the particle to the compound,thereby yielding said particle-delivery compound.

The functionalised compound may be any functionalised compound of theinvention as defined herein.

Step (a) of the process typically comprises contacting thefunctionalised compound with a substrate particle, more typically mixingthe substrate particle with the cross linking compound, optionally inthe presence of a solvent. Any suitable solvent may be used. Typically,the solvent is water. Mixing can be facilitated by sonication. When thefunctionalised compound used is a diazo compound, step (b) usuallycomprises heating the reaction mixture. Typically, the reaction mixtureis heated at the reflux temperature of the solvent employed. When thefunctionalised compound used is a hydrazone compound in which R¹ is H,this conversion may be achieved by oxidation of the hydrazone to adiazomethane followed by the application of energy, typically by heatingor by irradiation. In some embodiments, the functionalised compounds ofthe invention are heated to a temperature of from about 100° C. to about180° C., more typically from about 110° C. to 160° C., in order togenerate said carbene reactive intermediate groups. When thefunctionalised compound used is a sulfonylhydrazone compound, step (b)usually comprises heating the reaction mixture in the presence of abase. Any suitable base may be used, for instance an organic base suchas a trialkyl amine (e.g. triethylamine) or1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Alternatively an inorganicbase may be used, such as an alkali metal hydroxide, e.g. sodium,lithium or potassium hydroxide. Typically, the reaction mixture isheated at the reflux temperature of the solvent employed, and in someembodiments, it is heated to a temperature of from about 100° C. toabout 180° C., more typically from about 110° C. to 160° C., in order togenerate said carbene reactive intermediate groups.

The invention also provides a treated particle, which treated particlecomprises a substrate particle attached to a cross linking moiety offormula (XXVIVa):

wherein

C is a carbon atom;

* is a point of attachment of the carbon atom to the substrate particleor to another moiety or molecule; and

n, R, L and Q are as defined herein for the functionalised compound ofthe invention.

The treated particle may be a particle-delivery compound.

Typically, each * is a point of attachment of the cross linking moietyto a substrate particle or to another cross linking moiety of formula(XXVIVa).

In the treated particle or particle-delivery compound of the inventionas defined above, n, R, L and Q may be as further defined hereinbefore.

In one embodiment, the particle-delivery compound comprises a pluralityof substrate particles attached to a cross linking moiety of formula(XXVIVa).

Typically, the substrate particle used in the process of the inventionfor producing a treated particle or a particle-delivery compound, andthe substrate particle of the treated particle of the invention or theparticle-delivery compound of the invention, is a microparticle. Thesubstrate particle may alternatively be a nanoparticle.

As used herein, the term “microparticle” means a microscopic particlewhose size is measured in micrometers (μm). Typically, the microparticlehas an average diameter of from 1 μm to 1000 μm. More typically, themicroparticle has an average diameter of from 1 μm to 500 μm, forinstance from 1 μm to 250 μm. Most typically, the microparticle has anaverage diameter of from 1 μm to 100 μm.

As used herein, the term “nanoparticle” means a microscopic particlewhose size is measured in nanometers (nm). Typically, the nanoparticlehas an average diameter of from 1 nm to 1000 nm. More typically, thenanoparticle has an average diameter of from 5 nm to 500 μm, forinstance from 5 μm to 250 μm. Most typically, the nanoparticle has anaverage diameter of from 5 μm to 100 μm.

In one embodiment, the substrate particle is an encapsulate, i.e. aparticle which encapsulates one or more functional molecules, forinstance one or more perfume molecules. The encapsulate may itself be amicroparticle or a nanoparticle. Alternatively, the encapsulate may be amacroscopic beads. Typically, however, the encapsulate is a microscopicparticle, for instance a microparticle or a nanoparticle.

Typically, in this embodiment, the encapsulate is a perfume encapsulate,i.e. an encapsulate which comprises one or more perfume molecules. Suchperfume encapsulates are known and commercially available. Any suitableperfume encapsulate may be used. Suitable encapsulates are described inWO/2002/074430 (Quest International B.V.), which relates to perfumeencapsulates in which the capsule shell comprises a urea-formaldehyde ormelamine-formaldehyde polymer and a second polymer comprising a polymeror copolymer of one or more anhydrides, preferably ethylene/maleicanhydride copolymer. Further suitable encapsulates are described in U.S.Pat. No. 7,125,835 (International Flavors & Fragrances Inc.); EP1533364(International Flavours and Fragrances, Inc.); and U.S. Pat. No.7,294,612 (International Flavours and Fragrances, Inc.). U.S. Pat. No.7,294,612 describes a polymeric encapsulated fragrance which is suitablefor use in personal care and cleaning products. In another embodiment,the encapsulate is, or comprises, a fluorescent particle.

In another embodiment, the substrate particle is a fluorescent particle.

Typically, Q is a polymer. Typically, n is an integer equal to orgreater than 50, for instance equal to or greater than 100.

The polymer is typically one which provides the particle-deliverycompound with an affinity for a particular target material, thusfacilitating delivery of the particles to that target material.

In one embodiment, the target material is a fabric. The fabric may becotton or polyester, for instance. The inventors have shown that theattachment of perfume encapsulates and fluorescent encapsulates tofunctionalised cross linking compounds of formula (II), in which Qcomprises the polysaccharide locust bean gum, increases the depositionof the encapsulates onto cotton under wash cycle conditions.

Accordingly, in one embodiment Q comprises a polyester or apolysaccharide and the substrate particles are perfume encapsulates. Thepolyester may be Nylon, PET or POET, for instance. The polysaccharidemay be a galactomannan, for instance locust bean gum.

The point of attachment of the cross linking moiety of formula (XXVIVa)to the substrate particle or to another cross linking moiety of formula(XXVIVa), is depicted “*”. Thus, in the treated particles and inparticle-delivery compounds of the invention as defined above, thecarbon atom marked “*” is bonded to the substrate particle or to anothercross linking moiety of formula (XXVIVa). As the skilled person wouldunderstand, various different modes of binding of the cross linkingmoiety of formula (XXVIVa) to the substrate particle or to another crosslinking moiety of formula (XXVIVa) are possible via that carbon atom.For instance, the bond between the carbon atom marked “*” and an atom“Z” of the substrate particle (or an atom “Z” of another cross linkingmoiety of formula XXVIVa) may be a single covalent bond, in which casethat carbon atom is also bonded to another atom or group (for example ahydrogen atom), as follows:

Alternatively, the bond between the carbon atom marked “*” and an atom“Z” of the substrate particle (or an atom “Z” of another cross linkingmoiety of formula XXVIVa) may be a double bond, as follows:

Alternatively, the bond between the carbon atom marked “*” and an atom“Z” of the substrate particle (or an atom “Z” of another cross linkingmoiety of formula XXVIVa) may be a dative bond (also known as acoordinate bond), in which both electrons are provided by the carbonatom, as follows:

Alternatively, the carbon atom marked “*” may be bonded to two atoms,“Z” and “T”, of the substrate particle (or to two atoms, “Z” and “T”, ofanother cross linking moiety of formula (XXVIVa); or to one atom, “Z”,of the substrate particle and to another atom, “T”, of another crosslinking moiety of formula (XXVIVa)) wherein the bonds between the carbonatom marked “*” and the atoms Z and Z′ are both single bonds, asfollows:

The diazo-functionalised compounds of the invention can be used to crosslink two or more substrates, which two or more substrates may be thesame or different.

Accordingly, the invention provides a process for cross linking a firstsubstrate to a second substrate, which first and second substrates arethe same or different, which process comprises

(a) contacting the first and second substrates with a functionalisedcompound, wherein the functionalised compound is a functionalisedcompound of the invention as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that at least one carbene reactive intermediategroup reacts with the first substrate and at least one other reactiveintermediate group reacts with the second substrate, thereby crosslinking the first and second substrates.

The functionalised cross linking compound may be any functionalisedcompound of the invention as defined herein.

In one embodiment, the reactive intermediate precursor groups arecarbene precursor groups of formula (Ia), and the process for crosslinking a first substrate to a second substrate comprises

(a) contacting the first and second substrates with adiazo-functionalised cross linking compound, wherein thediazo-functionalised cross linking compound comprises n carbeneprecursor groups of formula (Ia), which are the same or different,wherein n is an integer equal to or greater than 2

wherein L is a single bond or a linker group and R is a terminal group;and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that at least one carbene reactive intermediategroup reacts with the first substrate and at least one other carbenereactive intermediate group reacts with the second substrate, therebycross linking the first and second substrates.

In another embodiment, the reactive intermediate precursor groups arehydrazone precursor groups of formula (Ie). More typically, they areprecursor groups of formula (Ie) in which R¹ is —S(O)₂R², wherein R² isas defined herein, i.e. sulfonylhydrazone groups.

As the skilled person will appreciate, typically some of the carbenereactive intermediate groups react with the first and second substratesand others react with other molecules of the cross linking compounditself.

In step (a), the first and second substrates may be contacted with thefunctionalised compound of the invention by any suitable method,depending on the physical forms of the first and second substrates. Forinstance, when the first and second substrates are both in particulateform, the particles may for instance be mixed with the functionalisedcompound of the invention to form a substantially homogeneous mixture.Alternatively, when the first and second substrates are both layers orsheets, the first and second substrates may be contacted with thefunctionalised compound of the invention by (i) applying a layer of thefunctionalised compound of the invention onto the first substrate, and(ii) subsequently applying a layer of the second substrate onto thefunctionalised compound of the invention. In another embodiment, thefirst and second substrates may be contacted with the functionalisedcompound of the invention by applying a mixture of the second substrateand the functionalised cross linking compound to the first substrate.

The functionalised compound of the invention may be applied as the neatcompound or in solution. Any suitable solvent may be used for thefunctionalised compound of the invention. Such suitable solvents includebut are not limited to alcohols, for instance methanol, methyl ethylketone and anisole.

The first or second substrate may for instance be contacted with thefunctionalised cross linking compound by dip coating, spray coating,rolling, printing or co-extrusion. The dip coating, spray coating,rolling, printing or co-extrusion may be performed in solution orotherwise. Thus, the dip coating, spray coating, rolling, printing orco-extrusion may be performed using a solution of the functionalisedcross linking compound or using the neat functionalised cross linkingcompound. Similarly, the dip coating, spray coating, rolling, printingor co-extrusion may be carried out using the neat first or secondsubstrate or using a suitable solution of the first or second substrate.

In step (b) of the process of the present invention for cross linking afirst substrate to a second substrate, the generated carbene reactiveintermediate groups may react with the surfaces of both the first andsecond substrates. In this context, the term “surface” means either thewhole of the surface of the substrate in question or only a portion ofthe surface of the substrate.

The carbene reactive intermediate groups are typically generated by athermal process, but may be generated chemically or by irradiation.Typically, the carbene reactive intermediate groups are generated byheating. This heat might be applied externally, but may also be as aresult of another process, for example, extrusion. Thus, step (b)usually comprises heating the reaction mixture. Typically, the reactionmixture is heated at the reflux temperature of the solvent employed. Insome embodiments, the mixture is heated to a temperature of from about100° C. to about 180° C., more typically from about 110° C. to 160° C.

When the functionalised compound used is a sulfonylhydrazone compound,step (b) usually comprises heating the reaction mixture in the presenceof a base. Any suitable base may be used, for instance an organic basesuch as a trialkyl amine (e.g. triethylamine) or1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Alternatively an inorganicbase may be used, such as an alkali metal hydroxide, e.g. sodium,lithium or potassium hydroxide. Typically, the reaction mixture isheated at the reflux temperature of the solvent employed or, forinstance, to a temperature of from about 100° C. to about 180° C., moretypically from about 110° C. to 160° C. When the functionalised compoundused is a hydrazone compound in which R¹ is H, this conversion may beachieved by oxidation of the hydrazone to a diazomethane followed by theapplication of energy, typically by heating to said temperature.

Less typically, the reactive intermediate may be generated byelectromagnetic radiation, for instance by UV, microwave or laserirradiation, or by ultrasonic irradiation. Some of these techniques,including laser and UV irradiation, are suitable for generation of thereactive intermediate selectively, i.e. on only a portion of the surfaceof the first or second substrate.

In one embodiment, only a portion of the surface of the first substrateis cross linked to a second substrate. For example, the surface of thefirst substrate may be modified in certain areas only, to form specifica “pattern” of cross linking. In this way, the two-dimensional shape ofthe resulting cross linked product may be controlled. This may be usefulin the design of printed circuit boards, for example, where the crosslinking of metal to substrate is only desired in certain specificplaces.

In one embodiment, the reactive intermediate groups are generatedselectively, i.e. only on certain portions of the surface of the firstsubstrate. In this way, only the particular regions of the surface onwhich the reactive intermediate has been generated become cross linkedto the second substrate. This is known as “selective activation”, andcan be used to form specific a “pattern” of cross linking.

Q in the functionalised cross linking compound used in the process ofthe invention for cross linking a first substrate to a second substratemay be a core moiety as defined hereinbefore; typically, n is an integerof from 3 to 20, or from 4 to 20, or from 3 to 10, or 4 to 10, or aninteger of 3, 4 or 5.

The invention also provides a cross-linked product comprising:

(a) a first substrate;

(b) a second substrate; and

(c) a cross linking moiety of formula (XXVIVa):

wherein

C is a carbon atom;

* is a point of attachment of the carbon atom to the first substrate,the second substrate, or to another moiety or molecule; and

n, R, L and Q are as defined herein for the functionalised compound ofthe invention.

Typically, each * is a point of attachment of the cross linking moietyto the first substrate, the second substrate or to another cross linkingmoiety of formula (XXVIVa). However, as the skilled person willappreciate, some of the carbon or nitrogen atoms, E′*, may be bonded tomolecules of other compounds too, if such other compounds were presentin the reaction mixture when the crosslinked product was formed.

As described above in relation to the treated particle andparticle-delivery compound of the invention, various different modes ofbinding of the cross linking moiety of formula (XXVIV) to the first andsecond substrates or to another cross linking moiety of formula (XXVIV)are possible via the carbene or nitrogen atom E′ marked “*”. Possiblebonding modes include those described above.

In the cross-linked product of the invention as defined above, R, L andQ may be as further defined hereinbefore. Usually, Q is a core moiety asdefined hereinbefore; typically, n is an integer of from 3 to 20, from 4to 20, or from 3 to 10, or from 4 to 10, or an integer of 3, 4 or 5.

The first and second substrates which are crosslinked in accordance withthe present invention may be the same material or two differentmaterials. Each substrate may be any natural or synthetic substratewhich is capable of reaction with a carbene reactive intermediate groupgenerated from a diazo-functionalised cross linking compound as definedabove, for instance from a diazo-functionalised compound of formula(II). Thus, a huge variety of first and second substrates may crosslinked in accordance with the present invention.

The first and second substrates, which are the same or different, mayfor instance be independently selected from any of the followingmaterials:

-   -   natural or synthetic polymers including but not limited to        cellulose, polyglycosides, polypeptides, polyacrylates,        polyacrylics, polyamides, polyimides, polycarbonates,        polyesters, epoxy resins, polyethers, polyketones, polyolefins,        rubbers, polystyrenics, polysulfones, polyurethanes, polyvinyls        and their co-polymers;    -   polyesters, polyacrylates, polyolefins, polyamides, polyimides,        polysulfones and epoxy resins, homopolymers and copolymers of        ethylene, propylene, styrene, PET (polyethylene terephthalate)        or EPDM (ethylene propylene diene monomer);    -   homopolymers and copolymers, for instance a block copolymers;    -   thermoplastic resins and thermosetting resins;    -   inorganic materials including but not limited to metals, metal        alloys, metal salts, silica, glasses, alumina, titania, and        allotropes of carbon such as diamond, diamond-like carbon,        graphite, fullerenes and nanotubes;    -   nanoparticles and microparticles;    -   C₆₀ and nanotubes, for instance carbon nanotubes;    -   textiles and paper.

The first substrate, or the second substrate, may comprise any two ormore of the above-listed materials.

The first and second substrates may be in any suitable physical form,and may be in the same form as one another or in different forms fromone another. Suitable forms include film, layer, sheet or board, powderform, pellet form or in the form of beads, particles, nanoparticles ormicroparticles. The pellets, beads or particles may be macroscopicparticles, i.e. visible to the naked eye, or microscopic particles.Thus, the particles could be microparticles or nanoparticles.

In one embodiment of the process of the invention for cross linking afirst substrate to a second substrate, or of the cross-linked product ofthe invention, the first substrate is a first polymer and the secondsubstrate is a second polymer. The first and second polymers, which maybe the same or different, may be independently selected from any ofthose listed above.

In one embodiment the first polymer is a hydrophilic polymer, forinstance poly(ethyleneimine). In another embodiment the first polymer isa hydrophobic polymer, for instance poly(tetrafluoroethylene). Thesecond polymer may be a polyester or a poly(alkylene) (for instancepolyethylene or polypropylene). In one embodiment, the second polymer isselected from poly(ethylene terephthalate) and polypropylene.

In another embodiment, the invention provides a process for producing achemically-bound three-dimensional network on or within a substrate,which process comprises:

(a) contacting a substrate with a functionalised compound of theinvention as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the substrate to produce said chemically-boundthree-dimensional network on or within the substrate.

The substrate may for instance be independently selected from any of thefollowing materials:

-   -   natural or synthetic polymers including but not limited to        cellulose, polyglycosides, polypeptides, polyacrylates,        polyacrylics, polyamides, polyimides, polycarbonates,        polyesters, epoxy resins, polyethers, polyketones, polyolefins,        rubbers, polystyrenics, polysulfones, polyurethanes, polyvinyls        and their co-polymers;    -   polyesters, polyacrylates, polyolefins, polyamides, polyimides,        polysulfones and epoxy resins, homopolymers and copolymers of        ethylene, propylene, styrene, PET (polyethylene terephthalate)        or EPDM (ethylene propylene diene monomer);    -   homopolymers and copolymers, for instance a block copolymers;    -   thermoplastic resins and thermosetting resins;    -   inorganic materials including but not limited to metals, metal        alloys, metal salts, silica, glasses, alumina, titania, and        allotropes of carbon such as diamond, diamond-like carbon,        graphite, fullerenes and nanotubes;    -   nanoparticles and microparticles;    -   C₆₀ and nanotubes, for instance carbon nanotubes;    -   textiles and paper.

In step (a), the substrate may be contacted with the functionalisedcompound of the invention by any suitable method, depending on thephysical form of the substrate. For instance, when the substrate is inparticulate form, the substrate may be mixed with the functionalisedcompound of the invention to form a substantially homogeneous mixture.Alternatively, when the substrate is a layer or sheet, the substrate maybe contacted with the functionalised compound of the invention byapplying a layer of the functionalised compound of the invention ontothe first substrate. In another embodiment, the substrate may be in theform of a melt, and the functionalised compound of the invention may becontacted with said melt.

The functionalised compound of the invention may be applied as the neatcompound or in solution. Any suitable solvent may be used for thefunctionalised compound of the invention.

In step (b) of the process of the present invention for producing achemically-bound three-dimensional network on or within a substrate, thegenerated carbene reactive intermediate groups react with the substrateto produce said chemically-bound three-dimensional network on or withinthe substrate. Thus, the generated carbene reactive intermediate groupsmay react with the bulk of the substrate, for instance in the case wherethe substrate is a melt or in solution, or just with the surface thesubstrate, for instance when the substrate is a solid material. In thiscontext, the term “surface” means either the whole of the surface of thesubstrate in question or only a portion of the surface of the substrate.The carbene reactive intermediate groups are typically generated by athermal process, but may be generated chemically or by irradiation.Typically, the carbene reactive intermediate groups are generated byheating. This heat might be applied externally, but may also be as aresult of another process, for example, extrusion. Thus, step (b)usually comprises heating the reaction mixture. Typically, the reactionmixture is heated at the reflux temperature of the solvent employed. Insome embodiments, the mixture is heated to a temperature of from about100° C. to about 180° C., more typically from about 110° C. to 160° C.When the functionalised compound used is a sulfonylhydrazone compound,step (b) usually comprises heating the reaction mixture in the presenceof a base. Any suitable base may be used, for instance an organic basesuch as a trialkyl amine (e.g. triethylamine) or1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Alternatively an inorganicbase may be used, such as an alkali metal hydroxide, e.g. sodium,lithium or potassium hydroxide. Typically, the reaction mixture isheated at the reflux temperature of the solvent employed or to atemperature of from about 100° C. to about 180° C., more typically fromabout 110° C. to 160° C. When the functionalised compound used is ahydrazone compound in which R¹ is H, the conversion may be achieved byoxidation of the hydrazone to a diazomethane followed by the applicationof energy, typically by heating or by irradiation.

In one embodiment of the process, the composition comprises:

-   -   (i) a substrate; and    -   (ii) a chemically-bound three-dimensional network on or within        the substrate, which chemically-bound three-dimensional network        is of formula (XXVIVa)

wherein:

C is a carbon atom;

* is a point of attachment of the carbon atom to the substrate or toanother molecule or moiety in the composition; and

n, R, L and Q are as defined in any one of claims 1 to 33,

and the process comprises:

(a) contacting a substrate with a functionalised compound as definedherein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the substrate to produce said composition.

The invention further provides a composition which comprises achemically-bound three-dimensional network on or within a substrate, thecomposition comprising:

-   -   a substrate; and    -   a chemically-bound three-dimensional network on or within the        substrate, which chemically-bound three-dimensional network is        of formula (XXVIVa)

wherein

C is a carbon atom;

* is a point of attachment of the carbon atom to the substrate or toanother molecule or moiety in the composition; and

n, R, L and Q are as defined herein.

The substrate may for instance be as defined above for the process ofthe invention for producing a chemically-bound three-dimensional networkon or within a substrate.

In another embodiment, the invention provides a process for producing achemically-bound three-dimensional network between a first substrate anda second substrate, which process comprises:

(a) contacting a first substrate and a second substrate with afunctionalised compound of the invention as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the first substrate and the second substrate to produce saidchemically-bound three-dimensional network between said first and secondsubstrates.

The first and second substrates may be any suitable substrates and maybe the same or different. They may for instance be independentlyselected from any of the materials listed above for the first and secondsubstrates of the cross linked product of the invention.

In step (a), the first and second substrates may be contacted with thefunctionalised compound of the invention by any suitable method,depending on the physical forms of the first and second substrates. Forinstance, when the first and second substrates are both in particulateform, the particles may for instance be mixed with the functionalisedcompound of the invention to form a substantially homogeneous mixture.Alternatively, when the first and second substrates are both layers orsheets, the first and second substrates may be contacted with thefunctionalised compound of the invention by (i) applying a layer of thefunctionalised compound of the invention onto the first substrate, and(ii) subsequently applying a layer of the second substrate onto thefunctionalised compound of the invention. In another embodiment, thefirst and second substrates may be contacted with the functionalisedcompound of the invention by applying a mixture of the second substrateand the functionalised cross linking compound to the first substrate.The functionalised compound of the invention may be applied as the neatcompound or in solution. Any suitable solvent may be used for thefunctionalised compound of the invention.

In one embodiment, the process for producing a chemically-boundthree-dimensional network between a first substrate and a secondsubstrate is a hot melt process, wherein step (a) comprises contacting amolten liquid comprising the first substrate and the second substratewith a functionalised compound of the invention as defined herein. Suchhot melt processes are exemplified herein.

Step (b) can be performed as described above for the process of theinvention for producing a chemically-bound three-dimensional network onor within a substrate.

In one embodiment of the process, the composition comprises:

-   -   a first substrate;    -   a second substrate; and    -   a three-dimensional network of formula (XXVIVa):

wherein

C is a carbon atom;

* is a point of attachment of the carbon atom to the first or secondsubstrate or to another molecule or moiety in said composition; and

n, R, L and Q are as defined herein for the functionalised compounds ofthe invention;

and the process comprises:

(a) contacting a first substrate and a second substrate with afunctionalised compound as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the first substrate and the second substrate to produce saidcomposition.

The invention further provides a composition which comprises:

-   -   a first substrate;    -   a second substrate; and    -   a three-dimensional network of formula (XXVIVa), which is bound        to said first and second substrates:

wherein

C is a carbon atom;

* is a point of attachment of the carbon atom to the first or secondsubstrate or to another molecule or moiety in said composition; and

n, R, L and Q are as defined herein for the functionalised compounds ofthe invention.

The invention further provides a process for producing a film or acoating, which process comprises:

(a) disposing a film formulation or a coating formulation onto thesurface of a substrate, which film or coating formulation comprises afunctionalised compound as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, thereby forming a film or a coating on said substrate.

In one embodiment, the process is for producing a film, and the processfurther comprises (c) removing said film from said substrate.

In another embodiment, the process is for producing a coated substratewhich comprises:

-   -   a substrate; and    -   a coating on a surface of the substrate, which coating comprises        a three-dimensional network of formula (XXVIVa):

wherein

C is a carbon atom;

* is a point of attachment of the carbon atom to the substrate or toanother molecule or moiety in the coating; and

n, R, L and Q are as defined herein for the functionalised compounds ofthe invention;

which process comprises:

(a) disposing a coating formulation onto the surface of a substrate,which coating formulation comprises a functionalised compound of theinvention as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, thereby forming a coating on said substrate.

Any suitable substrate can be used. The substrate may for instance beany of the materials listed above for the process of the invention forcross linking a first substrate to a second substrate.

The coating formulation used in step (a) typically comprises a furthermaterial, such as a second substrate, which may be the same as ordifferent from the (first) substrate. Typically, the second substrate isa polymer, but it may for instance be any of the substrate materialslisted above for the process of the invention for cross linking a firstsubstrate to a second substrate.

Typically, the coating formulation is a solution which comprises saidfurther material (second substrate) and said functionalised compound ofthe invention as defined herein, and a solvent.

In other embodiments, however, the coating formulation is a solutionwhich comprises said functionalised compound of the invention and asolvent, and step (a) comprises a first step of disposing said coatingformulation onto the surface of a substrate, and a second step ofdisposing a second solution onto the surface of a substrate, whichsecond solution comprises said further material (second substrate) and asolvent. More typically, in this embodiment, step (a) comprises a firststep of disposing said coating formulation onto the surface of asubstrate, to form a layer of said coating formulation thereon, a secondstep of allowing the resulting layer to dry, and a third step ofdisposing a second solution onto the surface of a substrate, whichsecond solution comprises said further material (second substrate) and asolvent.

Both of these alternatives are exemplified herein.

Step (b) can be carried out as described above for the processes of theinvention for producing a chemically-bound three-dimensional network onor within a substrate, for producing a chemically-boundthree-dimensional network between a first substrate and a secondsubstrate, and for cross linking a first substrate to a secondsubstrate.

The invention further provides a coated substrate which comprises:

-   -   a substrate; and    -   a coating on a surface of the substrate, which coating comprises        a three-dimensional network of formula (XXVIVa):

wherein

C is a carbon atom;

* is a point of attachment of the carbon atom to the substrate or toanother molecule or moiety in the coating; and

n, R, L and Q are as defined herein for the functionalised compounds ofthe invention.

The invention further provides a process for producing a product whichcomprises:

-   -   a first substrate;    -   a second substrate; and    -   a composition at an interface of the first and second        substrates, which composition comprises (i) a third material        and (ii) a three-dimensional network of formula (XXVIVa):

wherein

C is a carbon atom;

* is a point of attachment of the carbon atom to the first substrate,the second substrate, the third material, or to another molecule ormoiety in said composition; and

n, R, L and Q are as defined herein for the functionalised compounds ofthe invention;

which process comprises:

(a) providing a composition at an interface of a first substrate and asecond substrate, which composition comprises (i) a third material and(ii) a functionalised compound as defined herein; and

(b) generating carbene reactive intermediate groups from said carbeneprecursor groups, so that said carbene reactive intermediate groupsreact with the first substrate, the second substrate, and the thirdmaterial, to produce said product.

Any suitable first and second substrates can be used. The first andsecond substrates may be the same or different and may for instance beany of the materials listed above for the process of the invention forcross linking a first substrate to a second substrate.

The third material is typically a polymer or resin. It may for instancebe independently selected from any of the following materials:

-   -   natural or synthetic polymers including but not limited to        cellulose, polyglycosides, polypeptides, polyacrylates,        polyacrylics, polyamides, polyimides, polycarbonates,        polyesters, epoxy resins, polyethers, polyketones, polyolefins,        rubbers, polystyrenics, polysulfones, polyurethanes, polyvinyls        and their co-polymers;    -   polyesters, polyacrylates, polyolefins, polyamides, polyimides,        polysulfones and epoxy resins, homopolymers and copolymers of        ethylene, propylene, styrene, PET (polyethylene terephthalate)        or EPDM (ethylene propylene diene monomer);    -   homopolymers and copolymers, for instance a block copolymers;    -   thermoplastic resins and thermosetting resins.

The composition at the interface of the first and second substrate maybe a solution which comprises (i) said third material and (ii) saidfunctionalised compound as defined herein. Alternatively, however, thecomposition at the interface may be a dry film which comprises (i) saidthird material and (ii) said functionalised compound as defined herein.

Step (b) can be carried out as described above for the processes of theinvention for producing a chemically-bound three-dimensional network onor within a substrate, for producing a chemically-boundthree-dimensional network between a first substrate and a secondsubstrate, and for cross linking a first substrate to a secondsubstrate.

Further provided is a product which comprises:

-   -   a first substrate;    -   a second substrate; and    -   a composition at an interface of the first and second        substrates, which composition comprises (i) a third material        and (ii) a three-dimensional network of formula (XXVIVa):

wherein

C is a carbon atom;

* is a point of attachment of the carbon atom to the first substrate,the second substrate, the third material, or to another molecule ormoiety in said composition at said interface of the first and secondsubstrates; and

n, R, L and Q are as defined herein for the functionalised compounds ofthe invention.

Functionalised compounds of the invention of formula (II) may beproduced by the process of the invention as defined hereinbefore forproducing a functionalised compound of formula (II). Step (a) of theprocess comprises: (a) treating a first compound, Q′, which is a coremoiety, a polymer or a dendrimer and which bears n functional groups,with at least one second compound of formula (VIa)

wherein:

L′ is a leaving group or a reactive precursor to said group of formula(XII), wherein L′ is reactable with a said functional group to couplethe second compound to the first compound,

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl, and

Y is N═N, O or N—NHR¹, wherein R¹ is H or —S(O)₂R² and wherein R² is anunsubstituted or substituted C₁₋₆ alkyl group or an unsubstituted orsubstituted aryl group,

provided that when none of the [R]_(x)E-L- groups in the functionalisedcompound of formula (II) to be produced is a group of formula (Ie) inwhich R¹ is —S(O)₂R², then each L′ is a reactive precursor to said groupof formula (XII) and Q′ is a core moiety, a dendrimer, or a polymer,which polymer comprises: a polysaccharide, a protein, a polyester, apolyether, a polyacrylate, a polymethacrylate, a polycarbonate,polyetheretherketone (PEEK), a polyetherimide, a polyimide, apolysulfone, poly(vinyl chloride), a polysilane, a polysiloxane, apolyurea, a polyurethane, polylactic acid, polyvinylidene chloride, afluoro-polymer, a polyethylene imine, or a salt thereof.

Typically, the first compound Q′ which bears n functional groups istreated with at least n equivalents of the at least one second compoundof formula (VIa). As the skilled person will appreciate, however,functionalised compounds which comprise n carbene precursor groups offormula [R]_(x)-E-L-, all of which are the same, can be synthesised bytreating said first compound Q′ with at least n equivalents of a singlesecond compound of formula (VIa). In contrast, functionalised compoundswhich comprise n carbene precursor groups of formula [R]_(x)-E-L- notall of which are the same can be synthesised by treating said firstcompound Q′ with more than one type of second compound of formula (VIa).For instance, the first compound Q′ which bears n functional groups canbe treated with less than n equivalents of one compound of formula (VIa)and with less than n equivalents of another compound of formula (VIa),provided that the total number of equivalents of the compounds offormula (VIa) is at least n, to produce a functionalised compound of theinvention comprising two different types of reactive intermediateprecursor groups of formula [R]_(x)-E-L-.

The functionalised compound produced by the process of the invention isa compound of formula (II) which functionalised compound comprises ncarbene precursor groups which are the same or different, wherein n isan integer equal to or greater than 3

wherein x is 1, E is a group which is capable of being converted into acarbene reactive intermediate group, Q is a core moiety, a polymer or adendrimer, and each of the [R]_(x)-E-L- groups, which are the same ordifferent, is independently selected from a group of formula (Ie) and agroup of formula (Ia):

wherein

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

R¹ is —S(O)₂R² or H, wherein R² is an unsubstituted or substituted C₁₋₆alkyl group or an unsubstituted or substituted aryl group;

-   -   with the proviso that when none of the [R]_(x)-E-L- groups is a        group of formula (Ie) in which R¹ is —S(O)₂R², then:        -   each L is a group of formula (XII); and        -   Q is a core moiety, a dendrimer, or a polymer, which polymer            comprises: a polysaccharide, a protein, a polyester, a            polyether, a polyacrylate, a polymethacrylate, a            polycarbonate, polyetheretherketone (PEEK), a            polyetherimide, a polyimide, a polysulfone, poly(vinyl            chloride), a polysilane, a polysiloxane, a polyurea, a            polyurethane, polylactic acid, polyvinylidene chloride, a            fluoro-polymer, a polyethylene imine, or a salt thereof;

and the process comprises:

(a) treating a first compound, Q′, which is a core moiety, a polymer ora dendrimer and which bears n functional groups, with at least onesecond compound of formula (VIa)

wherein:

L′ is a leaving group or a reactive precursor to said group of formula(XII), wherein L′ is reactable with a said functional group to couplethe second compound to the first compound,

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ aryldi(C₁₋₂₀ alkyl)silyl, diaryl(C₁₋₂₀alkyl)silyl and triarylsilyl, and

Y is N═N, O or N—NHR¹, wherein R¹ is H or —S(O)₂R² and wherein R² is anunsubstituted or substituted C₁₋₆ alkyl group or an unsubstituted orsubstituted aryl group,

provided that when none of the [R]_(x)-E-L- groups in the functionalisedcompound of formula (II) to be produced is a group of formula (Ie) inwhich R¹ is —S(O)₂R², then each L′ is a reactive precursor to said groupof formula (XII) and Q′ is a core moiety, a dendrimer, or a polymer,which polymer comprises: a polysaccharide, a protein, a polyester, apolyether, a polyacrylate, a polymethacrylate, a polycarbonate,polyetheretherketone (PEEK), a polyetherimide, a polyimide, apolysulfone, poly(vinyl chloride), a polysilane, a polysiloxane, apolyurea, a polyurethane, polylactic acid, polyvinylidene chloride, afluoro-polymer, a polyethylene imine, or a salt thereof;

thereby producing a third compound of formula (IXa):

wherein Q, L, R, Y and n are as defined above;

provided that:

-   -   when Y is O, the process further comprises:        (b) treating the third compound with H₂N—NHR¹ in the presence of        heat, wherein R¹ is as defined above, thereby producing a fourth        compound of formula (X):

wherein Q, L, R, R¹ and n are as defined above; and, optionally,(c) converting some or all of the N—NHR¹ groups of said fourth compoundinto diazo groups, N═N;

and provided that:

-   -   when Y is N—NHR¹, the process optionally further comprises:        (b) converting some or all of the Y groups of said third        compound into diazo groups;

thereby producing said functionalised compound of formula (II).

The reaction conditions employed for step (a) depend on the particularstandard coupling chemistry which is used to couple or react Q′ with theleaving group or reactive precursor to L, denoted L′, in the compound offormula (VIa). The coupling chemistry employed will of course depend onthe particular terminal functional groups of Q′ and L′ that are reactedtogether (which include functional groups of formulae -A⁴-X² and -A³-Xrespectively, as defined hereinbefore) but standard coupling chemistrycan be used. For instance, the coupling of the Q′ functional groups tothe L′ group in the compound of formula (VIa) can be achieved byreaction between a triazine moiety derived from cyanuric chloride and ahydroxyl group; such a reaction is used in the synthesis of thetriazine-linked locust bean gum compound (6) in Example 1 hereinbelow.Alternatively, a reaction between an alkyl halide moiety and a hydroxylgroup may be employed, as is used in the synthesis of the ether-linkeddiazomethane locust bean gum compound (9) in Example 1 hereinbelow.Alternatively, an esterification-type reaction may be employed, such asa standard esterification reaction between an —OH group and a carboxylicacid group, or a reaction between an —OH group and an activatedcarboxylic acid moiety such as an acyl halide or an acid anyhydridemoiety. A coupling reaction between an acyl halide and a hydroxyl groupis employed in the synthesis of the tris(4-methyl diaryldiazomethane)1,3,5-benzene triester (19) in Example 1 hereinbelow. Alternatively, anaryl or heteroaryl group, such as a phenyl group, within Q′ can readilybe reacted with compounds of formula (VIa) in which L′ is a leavinggroup, for instance a chloro group. In particular, acyl chloridecompounds of formula (VIa) may react with aryl functional groups withina core moiety, polymer or dendrimer Q′ by Fridel-Crafts Acylation. Sucha reaction is well known in the art is described, for instance, in“Advanced Organic Chemistry; Reactions, Mechanisms, and Structure”,Jerry March, Fourth Edition, 1992, Wiley Interscience. A synthesisExample (synthesis of benzophenone modified polymer 25) is outlinedhereinbelow in Example 1. Typically, the Friedel-Crafts Acylation iscarried out in solution in the presence of aluminium trichloride. Manyother types of standard coupling reactions can however be employed inthe present invention, such as for instance the coupling of an aminogroup or a thiol group to a carboxylic acid or acyl halide group, or thereaction of a functional group with an alkene or an alkyne group. Suchstandard coupling reactions are also well known in the art and aredescribed, for instance, in “Advanced Organic Chemistry; Reactions,Mechanisms, and Structure”, Jerry March, Fourth Edition, 1992, WileyInterscience.

As explained hereinbefore, typically, Q′ has a functionality -A⁴-X² asdefined herein, for instance an OH, NH, SH or aryl (typically phenyl)functionality that allows single step transformation to introduce thecarbene precursor functionalities [R]_(x)-E-L- (or precursors thereof,[R]_(x)—C(O)-L-) onto Q.

Thus, in one embodiment, Q′ is a core moiety, polymer or dendrimer whichalready possesses at least n -A⁴-X² functionalities. The core moiety,polymer or dendrimer is therefore ready to react with the secondcompound of formula (VIa), in order to couple the second compound offormula (VIa) onto Q, in a single step.

Alternatively, however, a compound which does not bear any, or does notbear a sufficient number, n, of -A⁴-X² functionalities can besynthetically modified to attach -A⁴-X² functionalities, in order tosynthesise a core moiety, polymer or dendrimer, Q′, which has at least n-A⁴-X² functionalities.

An example of this second strategy is the modification of a polymer,core moiety or dendrimer which bears OH groups (for instance apolysaccharide, such as locust bean gum, or a polyester polymer) bytreating that polymer, core moiety or dendrimer with n equivalents ofcyanuric chloride in order to generate a modified polymer, core moietyor dendrimer, Q′, which bears n -A⁴-X² functionalities of the followingformula:

Accordingly, the process of the invention for producing a functionalisedcompound may further comprise the step of:

preparing said first compound, Q′, which bears n functional groups, byattaching said n functional groups to a precursor core moiety, aprecursor polymer or a precursor dendrimer.

Typically, the functional groups are groups of formula -A⁴-X² as definedherein.

Depending on the nature of Y in the compounds of formulae (VIa) and(IXa), the process of the invention for producing a functionalisedcompound may further comprise the steps of converting the ketonecompound, when Y is O, into a hydrazone compound, and optionallyconverting a hydrazone compound, when Y is N—NHR¹ into the correspondingdiazo compound.

Conversion of the ketone compound, when Y is O, into the correspondinghydrazone compound, where Y is N—NHR¹ is achieved by treating the ketonecompound with H₂N—NHR¹ in the presence of heat, wherein R¹ is as definedabove. Typically, the compound of formula (IXa) is treated with H₂N—NHR¹in the presence of heat and a solvent. Any suitable solvent may beemployed, for instance a polar protic solvent such as an alcohol.Typically, the solvent is methanol or ethanol. The reaction is carriedout with heating, typically at the reflux temperature of the solventused. For example, when the solvent is ethanol the reaction is suitablycarried out at a temperature of 78° C. or higher, e.g. at a temperatureof 80° C.

Conversion of the hydrazone compound, in which Y is N—NHR¹, into thecorresponding diazomethane compound, in which Y is N═N, is achieved byoxidation or elimination. Accordingly, in one embodiment the N—NHR¹groups of said third or fourth compound are converted into diazo groups,N═N, by oxidation or elimination. In the cases where R¹ is —S(O)₂R²,wherein R² is as defined above, an elimination reaction is performed.The elimination is typically achieved by treating the hydrazone compoundwith a basic compound such as an inorganic salt or a trialkylaminecompound or, for instance the organic base1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Usually, the inorganic salt islithium hydroxide, sodium hydroxide or potassium hydroxide. Usually, thetrialkylamine compound is triethylamine. DBU can be advantageous incertain applications as it is non-volatile. Typically, the treatment ofthe tosyl hydrazone compound with the base (for instance a trialkylaminecompound) is carried out in the presence of a solvent. The solvent usedis suitably a polar protic solvent such as an alcohol, for instancemethanol or water. The treatment can be carried out with the tosylhydrazone compound either in phase with the base, as a biphasic mixture,or as a suspension of tosyl hydrazone compound in a basic solution.

In the case where R¹ is H, an oxidation reaction is performed. Anysuitable oxidant can be used to convert the hydrazone compound, in whichY is N—NH₂, into the corresponding diazomethane compound. Suitableoxidants include metal oxides, such as mercuric oxide, nickel peroxide,or hydrogen peroxide or chlorine (bleach). Typically, the oxidant ismanganese oxide. More typically, this oxidation is conducted in thepresence of a base, for instance a metal hydroxide and sodium sulphate.The metal hydroxide is typically an alkali metal hydroxide, for instancepotassium hydroxide. A saturated solution of the metal hydroxide isgenerally used. The solvent used for the metal hydroxide is suitably apolar protic solvent such as an alcohol, for instance ethanol. Thesolvent used for the solution of the compound of formula (III) issuitably a polar aprotic solvent, for instance tetrahydrofuran (THF) oran ether.

In one embodiment, the functionalised compound is a hydrazone compoundof formula (XXX)

wherein:

n is an integer equal to or greater than 3;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²;

R¹ is H or —S(O)₂R², wherein R² is an unsubstituted or substituted C₁₋₆alkyl group or an unsubstituted or substituted aryl group; and

Q is a core moiety, a polymer or a dendrimer;

-   -   with the proviso that when R¹ is H, then:        -   each L is a group of formula (XII); and        -   Q is a core moiety, a dendrimer, or a polymer, which polymer            comprises: a polysaccharide, a protein, a polyester, a            polyether, a polyacrylate, a polymethacrylate, a            polycarbonate, polyetheretherketone (PEEK), a            polyetherimide, a polyimide, a polysulfone, poly(vinyl            chloride), a polysilane, a polysiloxane, a polyurea, a            polyurethane, polylactic acid, polyvinylidene chloride, a            fluoro-polymer, a polyethylene imine, or a salt thereof.

and the process comprises:

(a) treating a first compound, Q′, which is a core moiety, a polymer ora dendrimer and which bears at least n functional groups, with at leastone second compound of formula (VIa)

wherein:

L′ is a leaving group or a reactive precursor to said group of formula(XII), wherein L′ is reactable with a said functional group to couplethe second compound to the first compound,

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ aryldi(C₁₋₂₀ alkyl)silyl, diaryl(C₁₋₂₀alkyl)silyl and triarylsilyl, and

Y is O or N—NHR¹, wherein R¹ is as defined above, provided that when R¹is H, each L′ is a reactive precursor to said group of formula (XII) andQ′ is a core moiety, a dendrimer, or a polymer, which polymer comprises:a polysaccharide, a protein, a polyester, a polyether, a polyacrylate, apolymethacrylate, a polycarbonate, polyetheretherketone (PEEK), apolyetherimide, a polyimide, a polysulfone, poly(vinyl chloride), apolysilane, a polysiloxane, a polyurea, a polyurethane, polylactic acid,polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or asalt thereof;

thereby producing a third compound of formula (IXa):

wherein Q, L, R, Y and n are as defined above, wherein when Y is N—NHR¹said third compound is said hydrazone compound of formula (XXX);

provided that:

-   -   when Y is O, the process further comprises:        (b) treating the third compound with H₂N—NHR¹ in the presence of        heat, wherein R¹ is as defined above, provided that when R¹ is        H, each L′ is a reactive precursor to said group of        formula (XII) and Q′ is a core moiety, a dendrimer, or a        polymer, which polymer comprises: a polysaccharide, a protein, a        polyester, a polyether, a polyacrylate, a polymethacrylate, a        polycarbonate, polyetheretherketone (PEEK), a polyetherimide, a        polyimide, a polysulfone, poly(vinyl chloride), a polysilane, a        polysiloxane, a polyurea, a polyurethane, polylactic acid,        polyvinylidene chloride, a fluoro-polymer, a polyethylene imine,        or a salt thereof;

thereby producing said hydrazone compound of formula (XXX).

Typically, R¹ is —S(O)₂R², wherein R² is as defined herein. In anotherembodiment, R¹ is H.

Typically, the functionalised compound is a sulfonylhydrazone compoundof formula (XXXa)

wherein:

n is an integer equal to or greater than 3;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)allylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ diaryl(C₁₋₂₀alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a single bond or a group offormula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(R), wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²;

R² is an unsubstituted or substituted C₁₋₆ alkyl group or anunsubstituted or substituted aryl group; and

Q is a core moiety, a polymer or a dendrimer;

and the process comprises:

(a) treating a first compound, Q′, which is a core moiety, a polymer ora dendrimer and which bears at least n functional groups, with at leastone second compound of formula (VIb)

wherein:

L′ is a leaving group or a reactive precursor to said group of formula(XII), wherein L′ is reactable with a said functional group to couplethe second compound to the first compound, and

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₄₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

thereby producing a third compound of formula (IXb):

wherein Q, L, R and n are as defined above; and

(b) treating the third compound with H₂N—N(H)S(O)₂R² in the presence ofheat, wherein R² is an unsubstituted or substituted C₁₋₆ alkyl group oran unsubstituted or substituted aryl group, thereby producing saidsulfonylhydrazone compound of formula (XXXa).

In another embodiment, the functionalised compound is adiazo-functionalised compound of formula (IIa)

wherein:

n is an integer equal to or greater than 3;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ diaryl(C₁₋₂₀alkyl)silyl and triarylsilyl;

each L, which may be the same or different, is a group of formula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a dendrimer or a polymer, which polymer comprises: apolysaccharide, a protein, a polyester, a polyether, a polyacrylate, apolymethacrylate, a polycarbonate, polyetheretherketone (PEEK), apolyetherimide, a polyimide, a polysulfone, poly(vinyl chloride), apolysilane, a polysiloxane, a polyurea, a polyurethane, polylactic acid,polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or asalt thereof;

and the process comprises:

(a) treating a first compound, Q′, which bears n functional groups andwhich is a core moiety, a dendrimer or a polymer, which polymercomprises: a polysaccharide, a protein, a polyester, a polyether, apolyacrylate, a polymethacrylate, a polycarbonate, polyetheretherketone(PEEK), a polyetherimide, a polyimide, a polysulfone, poly(vinylchloride), a polysilane, a polysiloxane, a polyurea, a polyurethane,polylactic acid, polyvinylidene chloride, a fluoro-polymer, apolyethylene imine, or a salt thereof,

with at least one second compound of formula (VIa)

wherein:

L′ is a reactive precursor to said group of formula (XII), wherein L′ isreactable with a said functional group of the first compound, Q′, tocouple the second compound to the first compound,

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl, and

Y is N═N, O or N—NHR¹, wherein R¹ is H or —S(O)₂R² and wherein R² is anunsubstituted or substituted C₁₋₆ alkyl group or an unsubstituted orsubstituted aryl group;

thereby producing a third compound of formula (IXa):

wherein Q, L, R, Y and n are as defined above, wherein when Y is N═Nsaid third compound is said diazo-functionalised compound of formula(Ha);

provided that:

-   -   when Y is N—NHR¹, the process further comprises:        (b) converting the Y groups of said third compound into diazo        groups, thereby producing said diazo-functionalised compound of        formula (IIa);

and provided that:

-   -   when Y is O, the process further comprises:        (b) treating the third compound with H₂N—NHR¹ in the presence of        heat, wherein R¹ is as defined above, thereby producing a fourth        compound of formula (X):

wherein Q, L, R, R¹ and n are as defined above; and(c) converting the N—NHR¹ groups of said fourth compound into diazogroups, thereby producing said diazo-functionalised compound of formula(IIa).

The N—NHR¹ groups of said third or said fourth compound may be convertedinto diazo groups, N═N, by oxidation or elimination, as describedhereinbefore.

Typically, in the processes of the invention for producing afunctionalised compound, R² is an unsubstituted or substituted C₁₋₆alkyl group, an unsubstituted or substituted phenyl group, or anunsubstituted or substituted naphthyl group. Typically, R² is C₁₋₆alkyl, phenyl or naphthyl, which phenyl or naphthyl is unsubstituted orsubstituted with C₁₋₆ alkyl, di(C₁₋₆ alkyl)amino, hydroxyl, nitro, cyanoor methoxy. More typically, R² is C₁₋₆ alkyl, phenyl or naphthyl, whichphenyl or naphthyl is unsubstituted or substituted with C₁₋₆ alkyl ordi(C₁₋₆ alkyl)amino.

In another embodiment, the functionalised compound is a hydrazonecompound of formula (XXXb)

wherein:

n is an integer equal to or greater than 3;

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

each L, which is the same or different, is a group of formula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, *—Z²-arylene-O, *—Z²-heteroarylene-O,*—Z²—C₁₋₂₀ alkylene-O, *-arylene-O, *-heteroarylene-O, *—C₁₋₂₀alkylene-O, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O,*—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S,N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), whereineach R″ is independently selected from H, C₁₋₆ alkyl and aryl, andwherein * is the point of attachment of A³ to A²; and

Q is a core moiety, a dendrimer, or a polymer, which polymer comprises:a polysaccharide, a protein, a polyester, a polyether, a polyacrylate, apolymethacrylate, a polycarbonate, polyetheretherketone (PEEK), apolyetherimide, a polyimide, a polysulfone, poly(vinyl chloride), apolysilane, a polysiloxane, a polyurea, a polyurethane, polylactic acid,polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or asalt thereof;

and the process comprises:

(a) treating a first compound, Q′, which bears n functional groups andwhich is a core moiety, a dendrimer or a polymer, which polymercomprises: a polysaccharide, a protein, a polyester, a polyether, apolyacrylate, a polymethacrylate, a polycarbonate, polyetheretherketone(PEEK), a polyetherimide, a polyimide, a polysulfone, poly(vinylchloride), a polysilane, a polysiloxane, a polyurea, a polyurethane,polylactic acid, polyvinylidene chloride, a fluoro-polymer, apolyethylene imine, or a salt thereof,

with at least one second compound of formula (VIb)

wherein:

L′ is a reactive precursor to said group of formula (XII), wherein L′ isreactable with a said functional group of the first compound, Q′, tocouple the second compound to the first compound, and

R is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted orsubstituted by one, two, three, four or five groups, which groups arethe same or different and are independently selected from C₁₋₂₀ alkyl,C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀alkylamino, di(C₁₋₁₀)allylamino, arylamino, diarylamino, arylalkylamino,amido, acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy,haloalkyl, thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;

thereby producing a third compound of formula (IXb):

wherein Q, L, R and n are as defined above; and(b) treating the third compound with H₂N—NH₂ in the presence of heat,thereby producing said hydrazone compound of formula (XXXb).

Typically, in the process of the invention for producing afunctionalised compound, L′ is a group of formula (XI)

and L is a group of formula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl;

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S,N(R″), *—C(O)O, *—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀alkynylene, *—Z²—C₁₋₂₀ alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z²is selected from O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″)and N(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl, and wherein * is the point of attachment of A³ to A²;

and, in the group of formula (XI):

X is H, a halo group or a leaving group,

provided that when A³ is a single bond, *—Z²-arylene,*—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene, heteroarylene, C₁₋₂₀alkylene or S(O)₂, X is other than H and provided that when A³ is O, S,N(R″), —C(O)O—*, —C(O)N(R″)—* or —S(O)₂O—*, X is other than a halogroup.

In other embodiments, however, L is a single bond and L′ is a leavinggroup.

Typically, the n functional groups of the first compound, Q′, are groupsof formula -A⁴-X², wherein:

each A⁴, which is the same or different, is independently selected froma single bond, —Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀ alkylene-*,arylene, heteroarylene, C₁₋₂₀ alkylene, —Z³-arylene-O—*,—Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ alkylene-O—*, arylene-O—*,heteroarylene-O—*, C₁₋₂₀ alkylene-O—*, —C(O)—*, S(O)₂, —OC(O)—*,—N(R″)C(O)—*, O, S, N(R″), —C(O)O—*, —C(O)N(R″)—*, —S(O)₂O—*, C₁₋₂₀alkenylene, C₁₋₂₀ alkynylene, —Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀alkynylene-*, wherein Z³ is selected from O, S, N(R″), C(O), S(O),S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ isindependently selected from H, C₁₋₆ alkyl and aryl, and wherein * is thepoint of attachment of A⁴ to X²;

X² is H, a halo group or a leaving group;

provided that when A⁴ is a single bond, arylene, heteroarylene, C₁₋₂₀alkylene, —Z²-arylene-*, —Z²-heteroarylene-*, —Z²—C₁₋₂₀ alkylene-* orS(O)₂, X² is other than H and provided that when A⁴ is O, S, N(R″),—C(O)O—*, —C(O)N(R″)—*, —S(O)₂O—*, —Z³-arylene-O—*,—Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ alkylene-O—*, arylene-O—*,heteroarylene-O—* or C₁₋₂₀ alkylene-O—*, X² is other than a halo group;

and wherein Q comprises n linker groups of formula A⁴, each of which isattached to a group L, wherein each A⁴ is independently selected from asingle bond, —Z³-arylene-*, —Z³-heteroarylene-*, alkylene-*, arylene,heteroarylene, C₁₋₂₀ alkylene, —Z³-arylene-O—*, —Z³-heteroarylene-O—*,—Z³—C₁₋₂₀ alkylene-O—*, arylene-O—*, heteroarylene-O—*, C₁₋₂₀alkylene-O—*, —C(O)—*, S(O)₂, —OC(O)—*, —N(R″)C(O)—*, O, S, N(R″),—C(O)O—*, —C(O)N(R″)—*, —S(O)₂O—*, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene,—Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀ alkynylene-*, wherein Z³ isselected from O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″)and N(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl, and wherein * is the point of attachment of A⁴ to L.

In one embodiment, the n functional groups of said first compound, Q′,are the same.

In one embodiment of the process of the invention for producing afunctionalised compound, both Q and Q′ comprise a polymer or dendrimer,wherein the polymer is a linear polymer, a branched polymer, ahyperbranched polymer, a homopolymer, a copolymer or a block copolymer.The polymer may comprise a polysaccharide or a polyester or polystyrene,for instance.

Typically, in the process of the invention for producing afunctionalised compound, Q and Q′ comprise a polysaccharide, a protein,a polyester, a polyether, a polyacrylate, a polymethacrylate, apolycarbonate, polyetheretherketone (PEEK), a polyetherimide, apolyimide, a polysulfone, poly(vinyl chloride), a polysilane, apolysiloxane, a polyurea, a polyurethane, polylactic acid,polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or asalt thereof.

As mentioned above, in some embodiments, L is a single bond and L′ is aleaving group. The leaving group L′ may be a halo group, for instancechloro.

Typically, when L is a single bond and L′ is a leaving group, said nfunctional groups of Q′ are n aryl or heteroaryl rings, wherein Qcomprises said n aryl or heteroaryl rings, and wherein each L isattached directly to a said aryl or heteroaryl ring of Q, therebybonding the aryl or heteroaryl ring directly to the carbon atom which isbonded to R. Typically, in this embodiment the leaving group L′ in thecompound of formula (VIa) is a halo group, for instance chloro. Moretypically, L′ is chloro and Y in the compound of formula (VIa) is O, andthe coupling reaction in step (a) of the process of the inventionbetween Q′ and the compound of formula (VIa) is a Friedel-CraftsAcylation. Typically, the Friedel-Crafts Acylation is carried out insolution in the presence of aluminium trichloride. Typically, in thisembodiment Q′ and Q comprise a polymer that comprises said n aryl orheteroaryl rings. Usually said aryl or heteroaryl rings are aryl rings.The aryl rings are typically phenyl rings. Examples of polymers thatcomprise aryl rings include, for instance, polystyrene, a copolymercomprising polystyrene, a thermoplastic elastomer, polyisoprene, acopolymer comprising polyisoprene, SBS rubber, SIS rubber orpoly(styrene)-poly(ethylene/butylene)-poly(styrene) (SEBS).

Accordingly, when L is a single bond and L′ is a leaving group, Q′ istypically a polymer and said n functional groups of Q′ are n aryl orheteroaryl rings, wherein Q is a polymer which comprises said n aryl orheteroaryl rings and wherein each L which is single bond is attacheddirectly to a said aryl or heteroaryl ring of Q, thereby bonding thearyl or heteroaryl ring directly to the carbon atom which is bonded toR. Typically, said aryl or heteroaryl rings are aryl rings. Typically,said aryl rings are phenyl rings.

In one embodiment of the process of the invention, L is a single bond,L′ is a leaving group (for instance a halo group, e.g. chloro), Q′ is apolymer and said n functional groups of Q′ are n aryl or heteroarylrings, and Q is a polymer which comprises said n aryl or heteroarylrings, wherein each L which is single bond is attached directly to asaid aryl or heteroaryl ring of Q, thereby bonding the aryl orheteroaryl ring directly to the carbon atom which is bonded to R.Typically, said aryl or heteroaryl rings are aryl rings. Typically, saidaryl rings are phenyl rings. Typically, Q′ and Q comprise polystyrene, acopolymer comprising polystyrene, a thermoplastic elastomer,polyisoprene, a copolymer comprising polyisoprene, SBS rubber, SISrubber or poly(styrene)-poly(ethylene/butylene)-poly(styrene) (SEBS).

In one embodiment of the process of the invention Q′ is a core moiety, apolymer or a dendrimer which bears n aryl or heteroaryl groups, and Q isa core moiety, polymer or dendrimer comprising n linker moieties whichare arylene or heteroarylene groups, wherein each of said arylene orheteroarylene groups is attached to L.

Typically, Q′ and Q comprise polystyrene, a copolymer comprisingpolystyrene, a thermoplastic elastomer, polyisoprene, a copolymercomprising polyisoprene, SBS rubber, SIS rubber orpoly(styrene)-poly(ethylene/butylene)-poly(styrene) (SEBS).

In another embodiment, Q is a core moiety which is a straight-chained orbranched, saturated or unsaturated C₁₋₂₀ hydrocarbon moiety; an arylring; a heteroaryl ring; a C₅₋₁₀ carbocyclic ring; a C₅₋₁₀ heterocyclicring; or a fused bi-, tri- or tetracyclic ring system wherein each ringof said fused bi-, tri- or tetracyclic ring system is independentlyselected from an aryl ring, a heteroaryl ring, a C₅₋₁₀ carbocyclic ringand a C₅₋₁₀ heterocyclic ring; wherein said hydrocarbon moiety, arylring, heteroaryl ring, carbocyclic ring, heterocyclic ring or fused bi-,tri- or tetracyclic ring system is substituted with said n linkergroups, A⁴, and is otherwise unsubstituted or substituted, wherein eachA⁴ is attached to a group L, wherein A⁴ is as defined above,

and wherein Q′ is a straight-chained or branched, saturated orunsaturated C₁₋₂₀ hydrocarbon moiety; an aryl ring; a heteroaryl ring; aC₅₋₁₀ carbocyclic ring; a C₅₋₁₀ heterocyclic ring; or a fused bi-, tri-or tetracyclic ring system wherein each ring of said fused bi-, tri- ortetracyclic ring system is independently selected from an aryl ring, aheteroaryl ring, a C₅₋₁₀ carbocyclic ring and a C₅₋₁₀ heterocyclic ring;wherein said hydrocarbon moiety, aryl ring, heteroaryl ring, carbocyclicring, heterocyclic ring or fused bi-, tri- or tetracyclic ring system issubstituted with said n functional groups, -A⁴-X², and is otherwiseunsubstituted or substituted, wherein A⁴ and X² are as defined above.

Typically, Q′ is a compound of formula (XIII) and Q is a core moiety offormula (XIV)

wherein n is an integer of from 3 to 10, each A⁴ and each X² are thesame or different and are as defined above and wherein A is an arylring, a heteroaryl ring, a C₅₋₁₀ carbocyclic ring, a C₅₋₁₀ heterocyclicring, or a fused bi-, tri- or tetracyclic ring system wherein each ringof said fused bi-, tri- or tetracyclic ring system is independentlyselected from an aryl ring, a heteroaryl ring, a C₅₋₁₀ carbocyclic ringand a C₅₋₁₀ heterocyclic ring;

or wherein Q′ is a compound of formula (XV) and Q is a core moiety offormula (XVI)

wherein n is an integer of from 3 to 10, each A⁴ and each X² are thesame or different and are as defined above and wherein A^(HC) isstraight-chained or branched, saturated or unsaturated C₁₋₂₀ hydrocarbonmoiety which is otherwise unsubstituted or substituted.

Typically, in this embodiment, n is an integer of from 3 to 6.

Typically, in this embodiment, A is an aryl ring or a heteroaryl ring.

Typically, the C₁₋₂₀ hydrocarbon moiety is a straight-chained orbranched C₁₋₁₀ hydrocarbon moiety which is substituted with said n A⁴linkers and is otherwise unsubstituted or substituted. For instance, itmay be a methane, ethane, propane, butane, pentane, hexane, heptane,octane, nonane or decane moiety which is substituted with said n A⁴linkers and otherwise unsubstituted or substituted. The hydrocarbon maybe straight-chained or branched. Thus, for instance, a propanehydrocarbon moiety may be i-propane or n-propane and a butane moiety maybe t-butane, s-butane, i-butane or n-butane.

In one embodiment, n is 3.

Thus, more typically, Q′ is a compound of formula (XIIIa) and Q is acore moiety of formula (XIVa)

wherein each A⁴ and each X² are the same or different and are as definedabove and wherein A is an aryl or heteroaryl ring;or wherein Q′ is a compound of formula (XVa) and Q is a core moiety offormula (XVIa)

wherein each A⁴ and each X² are the same or different and are as definedabove and wherein q, m and p are the same or different and areindependently selected from 0 and an integer of 1 to 20.

In one embodiment of the process of the invention for producing afunctionalised compound, A³ is a single bond or an unsubstituted orsubstituted group selected from *—Z²-arylene, *—Z²-heteroarylene,*—Z²—C₁₋₂₀ alkylene, arylene, heteroarylene, C₁₋₂₀ alkylene, C(O),S(O)₂, *—OC(O) and *—N(R″)C(O), wherein Z² is selected from O, S, N(R″),C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein eachR″ is independently selected from H, C₁₋₆ alkyl and aryl, and wherein *is the point of attachment of A³ to A²; and, in the group of formula(XI), X is halo or a leaving group.

Typically, in this embodiment, A³ is a group of formula (XVII)

wherein * is the point of attachment of A³ to A², and wherein X^(L) ishalo, hydroxyl, C₁₋₁₀ alkoxy, C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl,aryl, aralkyl, cyano, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, acylamido, C₁₋₂₀haloalkyl, ester, acyl, acyloxy, aryloxy, nitro, carboxy, sulfonic acid,sulfonyl, sulphonamide, thiol, C₁₋₁₀ alkylthio or arylthio; and, in thegroup of formula (XI), X is halo (more typically Cl). Typically, X^(L)is halo or hydroxyl. More typically, X^(L) is halo, for instance chloro.

Even more typically, in this embodiment, A¹ is phenylene; A² is *—C₁₋₂₀alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 5 and wherein * isthe point of attachment of A² to A¹; and A³ is a group of formula (XVII)

wherein * is the point of attachment of A³ to A², X^(L) is as definedabove and, in the group of formula (XI), X is halo, for instance chloro.Thus, in a typical embodiment of the process of the invention forproducing a functionalised compound, L′ is:

and L is:wherein * is the point of attachment of L to the carbon atom bonded toR.

Alternatively, in this embodiment, A¹ is phenylene; A² is C₁₋₂₀alkylene; A³ is a single bond; and, in the group of formula (XI), X is ahalo group. Thus, L′ may be:

wherein * is the point of attachment of L to the carbon atom bonded toR.

Typically, in this embodiment, said first compound Q′ is a core moiety,a polymer or a dendrimer which bears n —OH groups; and wherein Q is acore moiety, polymer or dendrimer comprising n linker atoms which areoxygen atoms, wherein each of said oxygen atoms is attached to a groupL. More typically, first compound Q′ is a polysaccharide. Alternatively,the first compound Q′ may be a compound of formula (XIII) wherein Q is acore moiety of formula (XIV)

or the first compound Q′ may be a compound of formula (XV) and Q is acore moiety of formula (XVI)

wherein

A is an aryl or heteroaryl ring;

q, m and p are the same or different and are independently selected from0 and an integer of 1 to 20;

each A⁴ is the same or different and is independently selected from O,arylene-O—*, heteroarylene-O—*, C₁₋₂₀ alkylene-O—*, —Z³-arylene-O—*,—Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ alkylene-O—*, wherein Z³ is selectedfrom O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) andN(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆ alkyland aryl, wherein * is the point of attachment of A⁴ to X² or L; and X²is H. Alternatively, L is itself a single bond and, in the group offormula (XI), X is a leaving group, which is typically halo. Thus, X maybe chloro. Typically, in this embodiment, said first compound Q′ is acore moiety, a polymer or a dendrimer which bears n aryl or heteroarylgroups, typically n phenyl groups; and wherein Q is a core moiety,polymer or dendrimer comprising n linker atoms which are arylene orheteroarylene groups, typically phenylene groups, wherein each of saidarylene or heteroarylene groups is attached to L. More typically, thefirst compound Q′ is polystyrene. Q′ and Q may comprise polystyrene, acopolymer comprising polystyrene, a thermoplastic elastomer,polyisoprene, a copolymer comprising polyisoprene, SBS rubber, SISrubber or poly(styrene)-poly(ethylene/butylene)-poly(styrene) (SEBS).

In a different embodiment of the process of the invention for producinga functionalised compound, A³ is O, S, N(R″), *—C(O)O, *—C(O)N(R″),*—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀ alkenylene or*—Z²—C₁₋₂₀ alkynylene, wherein Z² is selected from O, S, N(R″), C(O),S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ isindependently selected from H, C₁₋₆ alkyl and aryl, and wherein * is thepoint of attachment of A³ to A²; and, in the group of formula (XI), X isH.

Typically, in this embodiment n A³ is O and, in the group of formula(XI), X is H. More typically, A¹ is phenylene; A² is C₁₋₂₀ alkylene; A³is O; and, in the group of formula (XI), X is H. Thus, usually, L′ is:

wherein * is the point of attachment of L to the carbon atom bonded toR.

Typically, in this embodiment of the process of the invention forproducing a functionalised compound, said first compound Q′ is a coremoiety, a polymer or a dendrimer which bears n groups of formula (XVIII)

wherein X^(L) is as defined above, X^(2L) is a halo group, typicallychloro, and Q is a core moiety, polymer or dendrimer which bears nlinker groups, each of which is attached to a group L, which linkergroups are of formula (XIX)

wherein * is the point of attachment to L and wherein X^(L) is asdefined above. Typically, the process further comprises producing saidfirst compound Q′ by treating a core moiety, a polymer or a dendrimer,which core moiety, polymer or dendrimer bears at least n —OH groups,with cyanuric chloride. More typically, the process further comprisesproducing said first compound Q′ by treating a polysaccharide or apolyester, which polysaccharide or polyester bears at least n —OHgroups, with cyanuric chloride.

Alternatively, in this embodiment of the process of the invention forproducing a functionalised compound, said first compound Q′ is acompound of formula (XIII) and Q is a core moiety of formula (XIV)

or Q′ is a compound of formula (XV) and Q is a core moiety of formula(XVI)

wherein

A is an aryl or heteroaryl ring;

q, m and p are the same or different and are independently selected from0 and an integer of 1 to 20;

each A⁴ is independently selected from a single bond, —Z³-arylene-*,—Z³-heteroarylene-*, —Z³—C₁₋₂₀ alkylene-*, arylene, heteroarylene, C₁₋₂₀alkylene, —C(O)—*, S(O)₂, —OC(O)—*, —N(R″)C(O)—*, C₁₋₂₀ alkenylene,C₁₋₂₀ alkynylene, —Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀ alkynylene-*,wherein Z³ is selected from O, S, N(R″), C(O), S(O), S(O)₂, C(O)O,OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ is independentlyselected from H, C₁₋₆ alkyl and aryl, and wherein * is the point ofattachment of A⁴ to X² or L; and

X² is a halo group.

Thus, the first compound Q′ may be:

In one embodiment of the process for of the invention for producing afunctionalised compound, at least one of the n functional groups of thefirst compound, Q′, is protected and the remaining functional group orgroups are unprotected, wherein L′ of said second compound of formula(VIa) or (VIb) is reactable with said unprotected functional group orgroups, to couple the second compound to the first compound, but notwith said at least one protected functional group, wherein step (a) ofthe process comprises:

-   -   (i) treating said first compound, Q′, with said second compound        of formula (VIa) or (VIb), thereby coupling the second compound        to the first via the unprotected functional group or groups;    -   (ii) deprotecting said at least one protected functional group;        and    -   (iii) treating the resulting compound with a compound of formula        (VIa) as defined herein, or with a compound of formula (VIb) as        defined herein, which is the same as or different from the        second compound used in step (i), thereby producing said third        compound.

Typically, in this embodiment, the unprotected functional groups arehydroxyl groups and the protected functional groups are protectedhydroxyl groups. The protected hydroxyl groups may protected by C₁₋₂₀alkyl groups (to form alkoxy groups) or by C₁₋₂₀ alkylene groups (toform —O—C₁₋₂₀ alkylene-O— groups). In the latter case, two protectedhydroxyl groups are protected by one and the same C₁₋₂₀ alkylene group.The C₁₋₂₀ alkylene group may be an isopropylidene group, for example.

Thus, in one embodiment of the process of the invention for producing afunctionalised compound, said first compound Q′ is a compound of formula(XXXIII) and Q is a core moiety of formula (XXXIV)

In this embodiment, the first compound Q′ bears one unprotected hydroxylfunctional group and two hydroxyl functional groups which are protectedwith an isopropylidene group. After the unprotected hydroxyl group isreacted with a second compound of formula (VIa) or (VIb), the twoprotected hydroxyl groups may be deprotected by hydrolysis. Typically,the hydrolysis is carried out in the presence of an acid. Typically, thehydrolysis is carried out in the presence of heat. The deprotectedhydroxyl groups are then reacted with a compound of formula (VIa) or(VIb), to produce said third compound in the process of the invention.

FURTHER ASPECTS OF THE DISCLOSURE

In a broader aspect, disclosed herein is a functionalised compound,which functionalised compound comprises n reactive intermediateprecursor groups of formula (I) which are the same or different, whereinn is an integer equal to or greater than 2

wherein x is 0 or 1, L is a single bond or a linker group, R is aterminal group and E is a reactive intermediate precursor functionality.

The term “reactive intermediate precursor functionality”, as usedherein, means a latent reactive group which is capable of beingconverted into a reactive intermediate group by a chemical process or bythe application of energy, wherein the reactive intermediate group iscapable of further reaction. The “application of energy” may forinstance involve the application of thermal energy (i.e. heating) orirradiation, although any suitable source of energy can be used.

Examples of reactive intermediate precursor functionalities, E, include,but are not limited to the following groups:

Thus, in one embodiment, E is a diazo, diazirine, azide or carbonylgroup.

Diazo and diazirine groups are “carbene precursor groups”, i.e. arecapable of conversion into carbene reactive intermediates, whereasnitrene groups are “nitrene precursor groups”, i.e. are capable ofconversion into nitrene reactive intermediates. Carbonyl groups on theother hand are precursors which are capable of being converted intoorganic radical reactive intermediates, for instance into any of thefollowing reactive intermediates:

As the skilled person will appreciate, whether the integer x is 1 or 2depends on the valency of the atom to which L and, when present, R, areattached. When that atom is a carbon atom (as it is in diazo, diazirineand carbonyl groups), x is 1, whereas when that atom is nitrogen (as itis in azide groups), x is 0.

Typically, the reactive intermediate employed is a carbene reactiveintermediate, a nitrene reactive intermediate or an organic radical.Thus, typically, each of the reactive intermediate precursorfunctionalities, E, is selected from: a group which is capable of beingconverted into a carbene reactive intermediate group; a group which iscapable of being converted into a nitrene reactive intermediate group;and a group which is capable of being converted into an organic radical.

Typically, the n reactive intermediate precursor groups of formula (I)are selected from:

carbene precursor groups, wherein x, L and R are as defined above and Eis a group which is capable of being converted into a carbene reactiveintermediate group;

nitrene precursor groups, wherein x, L and R are as defined above and Eis a group which is capable of being converted into a nitrene reactiveintermediate group; and

organic radical precursor groups, wherein x, L and R are as definedabove and E is a group which is capable of being converted into anorganic radical.

In one embodiment, the n reactive intermediate precursor groups offormula (I), which are the same or different, are selected from groupsof the following formula (Ia), (Ib), (Ic) and (Id):

wherein R and L are as defined above.

Typically, the n reactive intermediate precursor groups of formula (I)are diazo groups of formula (Ia), diazirine groups of formula (Ib) orazide groups of formula (Ic). More typically, the n reactiveintermediate precursor groups of formula (I) are diazo groups of formula(Ia) or diazirine groups of formula (Ib). Even more typically, the nreactive intermediate precursor groups of formula (I) are diazo groupsof formula (Ia).

The functionalised compound of the broader aspect as defined abovecomprises n reactive intermediate precursor groups of formula (I) whichare the same or different. Thus, although each of the n reactiveintermediate precursor groups falls within the formula (I) definition,the reactive intermediate precursor functionalities, E, the linkergroups (or single bonds) L, the integer x and/or the terminal groups Rwhen present, may differ from one reactive intermediate precursor groupto the next in the functionalised compound. For instance, thefunctionalised compound may comprise a first reactive intermediateprecursor group of formula (I) and a second reactive intermediateprecursor group of formula (I), wherein the reactive intermediateprecursor functionalities, E, the linker groups (or single bonds) L, theinteger x and/or the terminal groups R are different in the first andsecond reactive intermediate precursor groups. Typically, however, E isthe same reactive intermediate precursor functionality in all of theprecursor groups in the functionalised compound. Similarly, L istypically the same in all of the precursor groups in the functionalisedcompound. Similarly, R is typically the same terminal group in all ofthe precursor groups in the compound, and/or x is the same integer inall of those groups.

The number of reactive intermediate precursor groups in thefunctionalised compound, n, is an integer equal to or greater than 2.

Typically, however, n is greater than or equal to 3. In anotherembodiment, n is greater than or equal to 4.

In one embodiment, n is an integer of from 2 to 50 or from 3 to 50, moretypically an integer of from 2 to 20, from 2 to 10, from 3 to 20, orfrom 3 to 10, or an integer of 2, 3, 4 or 5.

In another embodiment, however, n is an integer of from 2 to 500, orfrom 3 to 500, and is more typically an integer of from 2 to 200, from 3to 200, from 2 to 100, from 3 to 100, or from 10 to 100, for instancefrom 10 to 50.

In yet another embodiment, n is an integer equal to or greater than 50,for instance equal to or greater than 100. Thus, n may be an integer offrom 50 to 1,000,000, from 50 to 100,000, from 50 to 10,000, from 50 to5,000, or from 50 to 1,000. More typically, in this embodiment, n is aninteger of from 50 to 1,000.

Typically, the functionalised compound of this broader aspect is acompound of formula (II)

wherein n is an integer equal to or greater than 2 (but may be asfurther defined herein); x is 0 or 1; L is a single bond or a linkergroup; R is a terminal group; E is reactive intermediate precursorfunctionality; and Q is a core moiety, a polymer or a dendrimer.

Again, the reactive intermediate precursor functionalities, E, thelinker groups (or single bonds) L, the terminal groups R, and theinteger x may differ from one reactive intermediate precursor group tothe next in the functionalised compound, but are typically the same.

Typically, each of the n reactive intermediate precursorfunctionalities, E, which are the same or different, is independentlyselected from: a group which is capable of being converted into acarbene reactive intermediate group; a group which is capable of beingconverted into a nitrene reactive intermediate group; and a group whichis capable of being converted into an organic radical.

In one embodiment, each of the [R]_(x)-E-L- groups in the functionalisedcompound of this broader aspect of formula (II), which are the same ordifferent, are independently selected from groups of the followingformula (Ia), (Ib), (Ic) and (Id):

wherein R and L are as defined above.

Typically, the [R]_(x)-E-L- groups in the functionalised compound ofthis broader aspect of formula (II) are selected from diazo groups offormula (Ia), diazirine groups of formula (Ib) and azide groups offormula (Ic). More typically, the [R]_(x)-E-L- groups in thefunctionalised compound of this broader aspect of formula (II) areselected from diazo groups of formula (Ia) and diazirine groups offormula (Ib). Even more typically, the [R]_(x)-E-L- groups in thefunctionalised compound of this broader aspect of formula (II) are diazogroups of formula (Ia).

In one embodiment, the compound is a diazo-functionalised compound,which diazo-functionalised compound comprises n carbene precursor groupsof formula (Ia) which are the same or different, wherein n is an integerequal to or greater than 2 (but may be as further defined herein):

wherein L is a single bond or a linker group and R is a terminal group.

The diazo-functionalised compound of the invention as defined abovecomprises n carbene precursor groups of formula (I) which are the sameor different. Thus, although each of the n carbene precursor groupsfalls within the formula (I) definition, the linker groups (or singlebonds) L, and/or the terminal groups R, may differ from one carbeneprecursor group to the next in the diazo-functionalised compound. Forinstance, the diazo-functionalised compound may comprise a first carbeneprecursor group of formula (I) and a second carbene precursor group offormula (I), wherein the terminal groups R and/or the linker groups (orsingle bonds) L are different in the first and second carbene precursorgroups. Typically, however, L is the same in all of the carbeneprecursor groups in the diazo-functionalised compound. Similarly, R istypically the same terminal group in all of the carbene precursor groupsin the compound.

Typically, the diazo-functionalised compound of the invention is acompound of formula (IIa)

wherein n is an integer equal to or greater than 2 (but may be asfurther defined herein); L is a single bond or a linker group; R is aterminal group; and Q is a core moiety, a polymer or a dendrimer. Again,the linker groups (or single bonds) L, and the terminal groups R, maydiffer from one carbene precursor group to the next in thediazo-functionalised compound, but are typically the same.

Each R group is typically selected from hydrogen, aryl, heteroaryl,C₁₋₂₀ perfluoroalkyl, C₁₋₁₀ alkoxy, aryloxy, di(C₁₋₁₀)alkylamino,alkylarylamino, diarylamino, C₁₋₁₀ alkylthio, arylthio and CR′₃, whereineach R′ is independently selected from a halogen atom, C₁₋₂₀ haloalkyl,C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, aryl, heteroaryl, C₃₋₂₀carbocyclyl, C₃₋₂₀ heterocyclyl, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀diaryl(C₁₋₂₀ alkyl)silyl, triarylsilyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl andC₁₋₂₀ alkyl, which C₁₋₂₀ alkyl and C₁₋₂₀ perfluoroalkyl are optionallyinterrupted by N(R″), O, S or arylene wherein R″ is H, C₁₋₆ alkyl oraryl; provided that when R is aryl or heteroaryl said aryl or heteroarylmay be unsubstituted or substituted by one, two, three, four or fivegroups, which groups are the same or different and are independentlyselected from C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroallyl, aryl, cyano, nitro,hydroxy, halo, carboxy, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, acyl, acyloxy, acylamido,ester, C₁₋₁₀ alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio,arylthio, sulfonic acid, sulfonyl, sulfonamide, tri(C₁₋₂₀ alkyl)silyl,aryldi(C₁₋₂₀ alkyl)silyl, diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl.

Each R group may be as further defined herein.

As to the nature of the groups L in the functionalised compound, anysuitable linking group may be employed or L may be a single bond.

Typically, however, each L, which may be the same or different, is agroup of formula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is a single bondor an unsubstituted or substituted group selected from arylene,heteroarylene, C₁₋₂₀ perfluoroalkylene, *—O—C₁₋₂₀ alkylene, *—O—C₁₋₂₀perfluoroalkylene, *—O-arylene, *—O-heteroarylene, *—N(R″)—C₁₋₂₀alkylene, *—N(R″)—C₁₋₂₀ perfluoroalkylene, *—N(R″)-arylene,*—N(R″)-heteroarylene, *—S—C₁₋₂₀ alkylene, *—S—C₁₋₂₀ perfluoroalkylene,*—S-arylene, *—S-heteroarylene, *—C(R′)₂—C₁₋₂₀ alkylene, *—C(R′)₂—C₁₋₂₀perfluoroalkylene, *—C(R′)₂-arylene, *—C(R′)₂-heteroarylene and C₁₋₂₀alkylene, wherein each R′ is independently selected from a halogen atom,C₁₋₁₀ haloalkyl, C₁₋₁₀ fluoroalkyl, C₁₋₁₀ perfluoroalkyl, aryl,heteroaryl, C₃₋₁₀ carbocyclyl, C₃₋₁₀ heterocyclyl, tri(C₁₋₁₀aryldi(C₁₋₁₀ alkyl)silyl, diaryl(C₁₋₁₀ alkyl)silyl, triarylsilyl, C₂₋₁₀alkenyl, C₂₋₁₀ alkynyl and C₁₋₁₀ alkyl, wherein * is the point ofattachment of A¹ to the carbon atom bonded to R, wherein each of saidC₁₋₂₀ alkylene and C₁₋₂₀ perfluoroalkylene groups is optionallyinterrupted by N(R″), O, S or arylene, and wherein R″ is H, C₁₋₆ alkylor aryl;

and A² and A³ are as defined hereinbefore.

A¹, A² and A³ may be as further defined hereinbefore.

In one embodiment A¹, A² and A³ are all single bonds, which means that Lis itself a single bond. Thus, in some embodiments, L is a single bondand each of the reactive intermediate precursor functionalities, E, isbonded directly to Q.

In one embodiment of the broader aspect, the functionalised compound isof formula (XXIIIa)

wherein Q and n are as defined hereinbefore. Typically in thisembodiment, Q is a core moiety, polymer or dendrimer bearing aryl orheteroaryl groups, more typically phenyl groups, wherein the carbon atomof the diazomethane group is bonded directly to said aryl or heteroarylgroups. More typically, in this embodiment, Q is polystyrene. Typically,the carbon atoms of the diazomethane groups are bonded to phenyl groupsof said polystyrene. In one embodiment of the broader aspect, thefunctionalised compound is of formula (XXVIa)

wherein n is an integer equal to or greater than 50.

The functionalised compounds of the broader aspects as defined above maybe as further defined herein for the functionalised compounds of theinvention.

Since the functionalised compounds of the broad aspect disclosed hereinbear at least 2 reactive intermediate precursor groups which can beconverted into reactive intermediate groups, one molecule of thefunctionalised compound can react with two or more molecules orparticles of a substrate compound, B, to form a cross link between themolecules or particles of B. Similarly, a molecule of the compound canform a cross link between two or more different compounds, e.g.compounds C and D. The functionalised compound can also react withitself intermolecularly, i.e. with other molecules of the functionalisedcompound. Thus, a bulk sample of the functionalised compound can reactboth with itself and with any other material or materials with which itis brought into contact, to form a cross-linked network that bonds thematerials together. For instance, a bulk layer of a functionalisedcompound may be applied between two substrates, E and F, and thereactive intermediate precursor groups of the functionalised compoundmay then be converted into reactive intermediate groups, thereby causingthe functionalised compound to react with itself intermolecularly and toreact with the surfaces of the two substrates, thereby forming across-linked network between E and F, bonding the two substratestogether.

Such substrates may be in any suitable physical form, for instance inthe form of a solution or suspension of the substrate, or in the form ofa solid film, layer, sheet or board. Alternatively, the substrates maybe in powder form, or in the form of pellets, beads, particles,nanoparticles or microparticles. The pellets, beads or particles may bemacroscopic particles, i.e. visible to the naked eye, or microscopicparticles. Thus, the particles could be microparticles or nanoparticles.

Accordingly, provided herein is the use of a functionalised compound asdefined herein, as a cross linking agent.

In another broad aspect, disclosed herein is a process for producing aparticle-delivery compound, which process comprises:

(a) contacting a functionalised cross linking compound with a substrateparticle, wherein the functionalised cross linking compound comprises nreactive intermediate precursor groups of formula (I) which are the sameor different, wherein n is an integer equal to or greater than 2

wherein x is 0 or 1, L is a single bond or a linker group, R is aterminal group and E is a reactive intermediate precursor functionality;and

(b) generating reactive intermediate groups from said reactiveintermediate precursor groups, so that a reactive intermediate groupreacts with the substrate particle to attach the particle to thecompound, thereby yielding said particle-delivery compound.

In another broad aspect, disclosed herein is a particle-deliverycompound, which particle-delivery compound comprises a substrateparticle attached to a cross linking moiety of formula (XXVIV)

wherein

E′ is a carbon or nitrogen atom;

* is a point of attachment of the cross linking moiety to the substrateparticle or to another moiety or molecule;

n is an integer equal to or greater than 2;

x is 1 when E′ is carbon and x is 0 when E′ is nitrogen;

each L, which is the same or different, is a single bond or a linkergroup;

each R, which is the same or different, is a terminal group; and

Q is a core moiety, a polymer or a dendrimer.

In another broad aspect, disclosed herein is a process for cross linkinga first substrate to a second substrate, which first and secondsubstrates are the same or different, which process comprises

(a) contacting the first and second substrates with a functionalisedcross linking compound, wherein the functionalised cross linkingcompound comprises n reactive intermediate precursor groups of formula(I) which are the same or different, wherein n is an integer equal to orgreater than 2

wherein x is 0 or 1, L is a single bond or a linker group, R is aterminal group and E is a reactive intermediate precursor functionality;and

(b) generating reactive intermediate groups from said reactiveintermediate precursor groups, so that at least one reactiveintermediate group reacts with the first substrate and at least oneother reactive intermediate group reacts with the second substrate,thereby cross linking the first and second substrates.

In another broad aspect, disclosed herein is a cross-linked productcomprising:

(a) a first substrate;

(b) a second substrate; and

(c) a cross linking moiety of formula (XXVIV)

wherein

the first and second substrates are the same or different,

E′ is a carbon or nitrogen atom;

each * is a point of attachment of the cross linking moiety to the firstsubstrate, the second substrate or to another moiety or molecule;

n is an integer equal to or greater than 2;

x is 1 when E′ is carbon and x is 0 when E′ is nitrogen;

each L, which is the same or different, is a single bond or a linkergroup;

each R, which is the same or different, is a terminal group; and

Q is a core moiety, a polymer or a dendrimer.

In another broad aspect, disclosed herein is a process for producing afunctionalised compound, which functionalised compound comprises nreactive intermediate precursor groups of formula (I) which are the sameor different, wherein n is an integer equal to or greater than 2

wherein x is 0 or 1, L is a single bond or a linker group, R is aterminal group and E is a reactive intermediate precursor functionality,

the process comprising:

(a) treating a first compound which bears n functional groups, with atleast one second compound of formula (VI)

wherein:

L′ is a leaving group or a reactive precursor to said linker group,wherein L′ is reactable with a said functional group to couple thesecond compound to the first compound,

R is said terminal group and x is 0 or 1, and

E^(P) is said reactive intermediate precursor functionality E or aprecursor thereto,

thereby producing a third compound which comprises n groups of formula(VII):

wherein L is said single bond or linker group, R is said terminal group,x is 0 or 1, and E^(P) is as defined above, which third compound is saidfunctionalised compound when E^(P) is said reactive intermediateprecursor functionality E;provided that:

when E^(P) is a precursor to said reactive intermediate precursorfunctionality E, the process further comprises:

(b) converting the groups of formula (VII) of said third compound intoreactive intermediate precursor groups of formula (I), thereby producingsaid functionalised compound.

Typically, the first compound which bears n functional groups is treatedwith at least n equivalents of the at least one second compound offormula (VI). As the skilled person will appreciate, however,functionalised compounds which comprise n reactive intermediateprecursor groups of formula (I) all of which are the same can besynthesised by treating said first compound with at least n equivalentsof a single second compound of formula (VI). In contrast, functionalisedcompounds which comprise n reactive intermediate precursor groups offormula (I) not all of which are the same can be synthesised by treatingsaid first compound with more than one type of second compound offormula (VI). For instance, the first compound which bears n functionalgroups can be treated with less than n equivalents of one compound offormula (VI) and with less than n equivalents of another compound offormula (VI), provided that the total number of equivalents of thecompounds of formula (VI) is at least n, to produce a functionalisedcompound comprising two different types of reactive intermediateprecursor groups of formula (I).

Typically, the functionalised compound produced is a compound of formula(II)

wherein n is an integer equal to or greater than 2; x is 0 or 1; L is asingle bond or a linker group; R is a terminal group; E is reactiveintermediate precursor functionality; and Q is a core moiety, a polymeror a dendrimer,

and the process comprises:

(a) treating a first compound, Q′, which is a core moiety, a polymer ora dendrimer and which bears n functional groups, with at least onesecond compound of formula (VI)

wherein:

L′ is a leaving group or a reactive precursor to said linker group,wherein L′ is reactable with a said functional group to couple thesecond compound to the first compound,

R is said terminal group and x is 0 or 1, and

E^(P) is said reactive intermediate precursor functionality E or aprecursor thereto, thereby producing a third compound which is offormula (IX):

wherein L is said single bond or linker group, R is said terminal group,x is 0 or 1, and E^(P) is as defined above, which third compound is saidfunctionalised compound of formula (II) when E^(P) is said reactiveintermediate precursor functionality E;provided that:

when E^(P) is a precursor to said reactive intermediate precursorfunctionality E, the process further comprises:

(b) converting the E^(P) groups of said third compound into reactiveintermediate precursor groups, E, thereby producing said functionalisedcompound of formula (II).

Typically, each of the n reactive intermediate precursorfunctionalities, E, which are the same or, different, is independentlyselected from: a group which is capable of being converted into acarbene reactive intermediate group; a group which is capable of beingconverted into a nitrene reactive intermediate group; and a group whichis capable of being converted into an organic radical.

In one embodiment, each of the [R]_(x)-E-L- groups in the functionalisedcompound of formula (II), which are the same or different, areindependently selected from groups of the following formula (Ia), (Ib),(Ic) and (Id):

wherein R and L are as defined above.

Typically, the [R]_(x)-E-L- groups in the functionalised compound offormula (II) are selected from diazo groups of formula (Ia), diazirinegroups of formula (Ib) and azide groups of formula (Ic). More typically,the [R]_(x)-E-L- groups in the functionalised compound of formula (II)are selected from diazo groups of formula (Ia) and diazirine groups offormula (Ib).

Even more typically, the [R]_(x)-E-L- groups in the functionalisedcompound of formula (II) are diazo groups of formula (Ia).

Accordingly, disclosed herein is a process for producing adiazo-functionalised compound, which diazo-functionalised compoundcomprises n carbene precursor groups of formula (Ia), which are the sameor different, wherein n is an integer equal to or greater than 2

wherein L is a single bond or a linker group and R is a terminal group,the process comprising:(a) treating a first compound which bears n functional groups, with atleast one second compound of formula (VIa)

wherein:

L′ is a leaving group or a reactive precursor to said linker group,wherein L′ is reactable with a said functional group to couple thesecond compound to the first compound,

R is said terminal group, and

Y is N═N, O or N—NHR¹, wherein R¹ is H or —S(O)₂R² and wherein R² isC₁₋₆ alkyl, phenyl or naphthyl, which phenyl or naphthyl isunsubstituted or substituted with C₁₋₆ alkyl or di(C₁₋₆ alkyl)amino,

thereby producing a third compound which comprises n groups of formula(VIIa):

wherein L is said single bond or linker group, R is said terminal groupand Y is as defined above, which third compound is saiddiazo-functionalised compound when Y is N═N;provided that:

-   -   when Y is N—NHR¹, the process further comprises:        (b) converting the groups of formula (VIIa) of said third        compound, by oxidation or elimination, into carbene precursor        groups of formula (Ia), thereby producing said        diazo-functionalised compound; and provided that:    -   when Y is O, the process further comprises:        (b) treating the third compound with H₂N—NHR¹ in the presence of        heat, wherein R¹ is as defined above, thereby producing a fourth        compound which comprises n groups of formula (VIII):

wherein L is said single bond or linker group, R is said terminal groupand R¹ is as defined above; and(c) converting the groups of formula (VIII) of said fourth compound, byoxidation or elimination, into carbene precursor groups of formula (Ia),thereby producing said diazo-functionalised compound.

Typically, the diazo-functionalised compound produced by the process isa compound of formula (IIa)

wherein:

n is an integer equal to or greater than 2;

each L is a single bond or a linker group;

each R is a terminal group; and

Q is a core moiety, a polymer or a dendrimer;

and the process comprises:

(a) treating a first compound, Q′, which is a core moiety, a polymer ora dendrimer and which bears n functional groups, with at least onesecond compound of formula (VIa)

wherein:

L′ is a leaving group or a reactive precursor to said linker group,wherein L′ is reactable with a said functional group to couple thesecond compound to the first compound,

R is said terminal group, and

Y is N═N, O or N—NHR¹, wherein R¹ is H or —S(O)₂R² and wherein R² isC₁₋₆ alkyl, phenyl or naphthyl, which phenyl or naphthyl isunsubstituted or substituted with C₁₋₆ alkyl or di(C₁₋₆ alkylamino,

thereby producing a third compound of formula (IXa):

wherein Q, L, R, Y and n are as defined above, which third compound issaid diazo-functionalised compound when Y is N═N;provided that:

-   -   when Y is N—NHR¹, the process further comprises:        (b) converting the Y groups of said third compound, by oxidation        or elimination, into diazo groups, thereby producing said        diazo-functionalised compound of formula (IIa); and        provided that:    -   when Y is O, the process further comprises:        (b) treating the third compound with H₂N—NHR¹ in the presence of        heat, wherein R¹ is as defined above, thereby producing a fourth        compound of formula (X):

wherein Q, L, R, R¹ and n are as defined above; and(c) converting the N—NHR¹ groups of said fourth compound, by oxidationor elimination, into diazo groups, thereby producing saiddiazo-functionalised compound of formula (IIa).

Typically, in the disclosed process for producing a functionalisedcompound, L′ is a group of formula (XI)

and L is a group of formula (XII)

wherein:

A¹ is bonded to the carbon atom bonded to R, wherein A¹ is a single bondor an unsubstituted or substituted group selected from arylene,heteroarylene, C₁₋₂₀ perfluoroalkylene, *—O—C₁₋₂₀ alkylene, *—O—C₁₋₂₀perfluoroalkylene, *—O-arylene, *—O-heteroarylene, *—N(R″)—C₁₋₂₀alkylene, *—N(R″)—C₁₋₂₀ perfluoroalkylene, *—N(R″)-arylene,*—N(R″)-heteroarylene, *—S—C₁₋₂₀ alkylene, *—S—C₁₋₂₀ perfluoroalkylene,*—S-arylene, *—S-heteroarylene, *—C(R′)₂—C₁₋₂₀ alkylene, *—C(R′)₂—C₁₋₂₀perfluoroalkylene, *—C(R′)₂-arylene, *—C(R′)₂-heteroarylene and C₁₋₂₀alkylene, wherein each R′ is independently selected from a halogen atom,C₁₋₁₀ haloalkyl, C₁₋₁₀ fluoroalkyl, C₁₋₁₀ perfluoroalkyl, aryl,heteroaryl, C₃₋₁₀ carbocyclyl, C₃₋₁₀ heterocyclyl, tri(C₁₋₁₀alkyl)silyl, aryldi(C₁₋₁₀ diaryl(C₁₋₁₀ alkyl)silyl, triarylsilyl, C₂₋₁₀alkenyl, C₂₋₁₀ alkynyl and C₁₋₁₀ alkyl, wherein * is the point ofattachment of A¹ to the carbon atom bonded to R, wherein each of saidC₁₋₂₀ alkylene and C₁₋₂₀ perfluoroalkylene groups is optionallyinterrupted by N(R″), O, S or arylene, and wherein R″ is H, C₁₋₆ alkylor aryl;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl;

A³ is a single bond or an unsubstituted or substituted group selectedfrom *—Z²-arylene, *—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene,heteroarylene, C₁₋₂₀ alkylene, C(O), S(O)₂, *—OC(O), *—N(R″)C(O), O, S,N(R″), *—C(O)O, *—C(O)N(R″), *—S(O)₂O, C₁₋₂₀ alkenylene, C₁₋₂₀alkynylene, *—Z²—C₁₋₂₀ alkenylene and *—Z²—C₁₋₂₀ alkynylene, wherein Z²is selected from O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″)and N(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl, and wherein * is the point of attachment of A³ to A²;

and, in the group of formula (XI):

X is H, a halo group or a leaving group,

provided that when A³ is a single bond, *—Z²-arylene,*—Z²-heteroarylene, *—Z²—C₁₋₂₀ alkylene, arylene, heteroarylene, C₁₋₂₀alkylene or S(O)₂, X is other than H and provided that when A³ is O, S,N(R″), —C(O)O—*, —C(O)N(R″)—* or —S(O)₂O—*, X is other than a halogroup.

In one embodiment of the process for producing a functionalisedcompound, at least one of the n functional groups of the first compound,Q′, is protected and the remaining functional group or groups areunprotected, wherein L′ of said second compound of formula (VI) or (VIa)is reactable with said unprotected functional group or groups, to couplethe second compound to the first compound, but not with said at leastone protected functional group, wherein step (a) of the processcomprises:

-   -   (i) treating said first compound, Q′, with said second compound        of formula (VI) or (VIa), thereby coupling the second compound        to the first via the unprotected functional group or groups;    -   (ii) deprotecting said at least one protected functional group;        and    -   (iii) treating the resulting compound with a compound of        formula (VI) or (VIa), which is the same as or different from        the second compound used in step (i), thereby producing said        third compound.

The process may be as further defined herein for the process of theinvention.

In another broad aspect, disclosed herein is a hydrazone compound offormula (XXX)

wherein:

n is an integer equal to or greater than 2;

each L, which is the same or different, is a single bond or a linkergroup;

each R, which is the same or different, is a terminal group;

R¹ is H or —S(O)₂R², wherein R² is C₁₋₆ alkyl, phenyl or naphthyl, whichphenyl or naphthyl is unsubstituted or substituted with C₁₋₆ alkyl ordi(C₁₋₆ alkyl)amino; and

Q is a core moiety, a polymer or a dendrimer.

R, L, Q, n and R¹ may be as further defined herein.

In another broad aspect, disclosed herein is a ketone compound offormula (XXXI)

wherein:

n is an integer equal to or greater than 2;

each L, which is the same or different, is a single bond or a linkergroup;

each R, which is the same or different, is a terminal group; and

Q is a core moiety, a polymer or a dendrimer.

R, L, Q and n may be as further defined herein.

In one embodiment, the ketone compound is a compound of formula (XXXII)

wherein

R is a terminal group;

A¹ is a single bond or an unsubstituted or substituted group selectedfrom arylene, heteroarylene, C₁₋₂₀ perfluoroalkylene, *—O—C₁₋₂₀alkylene, *—O—C₁₋₂₀ perfluoroalkylene, *—O-arylene, *—O-heteroarylene,*—N(R″)—C₁₋₂₀ alkylene, *—N(R″)—C₁₋₂₀ perfluoroalkylene,*—N(R″)-arylene, *—N(R″)-heteroarylene, *—S—C₁₋₂₀ alkylene, *—S—C₁₋₂₀perfluoroalkylene, *—S-arylene, *—S-heteroarylene, *—C(R′)₂—C₁₋₂₀alkylene, *—C(R′)₂—C₁₋₂₀ perfluoroalkylene, *—C(R′)₂-arylene,*—C(R′)₂-heteroarylene and C₁₋₂₀ alkylene, wherein each R′ isindependently selected from a halogen atom, C₁₋₁₀ haloalkyl, C₁₋₁₀fluoroalkyl, C₁₋₁₀ perfluoroalkyl, aryl, heteroaryl, C₃₋₁₀ carbocyclyl,C₃₋₁₀ heterocyclyl, tri(C₁₋₁₀ alkyl)silyl, aryldi(C₁₋₁₀ alkyl)silyl,diaryl(C₁₋₁₀ alkyl)silyl, triarylsilyl, C₂₋₁₀ alkenyl, C₂₋₁₀ alkynyl andC₁₋₁₀ alkyl, wherein * is the point of attachment of A¹ to the carbonylcarbon atom bonded to R, wherein each of said C₁₋₂₀ alkylene and C₁₋₂₀perfluoroalkylene groups is optionally interrupted by N(R″), O, S orarylene, and wherein R″ is H, C₁₋₆ alkyl or aryl;

A² is a single bond or an unsubstituted or substituted group selectedfrom C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene, heteroarylene,*—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1 to 20,*—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and

each Z¹ is a halo group.

In one embodiment, the ketone compound is of formula (XXXII), and R, A¹and A² are as further defined hereinbefore. Typically, both Z¹ groupsare chloro, bromo or iodo groups. More typically, both Z¹ groups arechloro groups.

In one embodiment the ketone compound has the following formula:

The invention is further described in the following Examples:

EXAMPLES Example 1 Synthesis of Chemical Agents Capable of 3-D NetworkFormation Route 1 Synthesis of Triazine Linked Diazomethane Locust BeanGum, with Reference to FIG. 1 Synthesis of 4-methyl-4′-nitrobenzophenone(1)

4-Nitrobenzoyl chloride (5.00 g, 26.0 mmol, 1 eq) was suspended intoluene (10 mL) and the cloudy yellow mixture was cooled to 0° C. in anice/water bath. Aluminium trichloride (4.50 g, 33.7 mmol, 1.25 eq) wasadded portionwise over a period of 20 min and the mixture was allowed towarm to room temperature. After stirring at room temperature for 2 hrHPLC indicated that the starting material had been consumed. Thereaction was quenched by pouring onto an ice/1 M HCl solution where theproduct precipitated out as a yellow solid. The aqueous mixture wasextracted with ethyl acetate (3×50 mL). The organic washings were driedover magnesium sulfate and concentrated under reduced pressure to give ayellow solid. The yellow solid was recrystallised from 2-propanol togive 4-methyl-4′-nitrobenzophenone (4.05 g, 62% yield) as a yellowcrystalline solid.

Synthesis of 4-bromomethyl-4′-nitrobenzophenone (2)

4-Methyl-4′nitrobenzophenone (46.80 g, 194.0 mmol, 1 eq) was dissolvedin chloroform (400 mL) giving a pale yellow solution. N-Bromosuccinimide(69.10 g, 388.0 mmol, 2.0 eq) was then added portionwise over 5 minturning the solution cloudy. The mixture was heated to reflux andstirred for 7 hr and allowed to cool. The mixture was left to stand for18 hr and then heated under reflux for a further 3 hr. After this timeHPLC indicated that most of the starting material had been consumed andthe 4-dibromomethyl-4′-nitrobenzophenone was forming as a side product.The reaction mixture was cooled, washed with saturated sodiumthiosulfate solution (2×200 mL) and dried over magnesium sulfate. Thesolution was concentrated under reduced pressure to give a beige solid.The solid was recrystallised from 30% petroleum ether/ethyl acetate togive 4-bromomethyl-4′-nitrobenzophenone (26.25 g, 42%)

Synthesis of 4-hydroxymethyl-4′-nitrobenzophenone (3)

4-bromomethyl-4′-nitrobenzophenone (3.20 g, 10.0 mmol, 1 eq) wasdissolved in a 2:1 acetonitrile/water mixture (300 mL) and calciumcarbonate (3.00 g, 30.0 mmol, 3 eq) was added. The turbid mixture wasstirred under reflux for 60 hr. After this time the reaction mixture wasallowed to cool and the solid calcium carbonate was filtered off. Thesolid was washed with ethyl acetate (10 mL) and the filtrate wasconcentrated under reduced pressure to give an off-white solid. Thesolid was dissolved in ethyl acetate and washed with concentratedhydrochloric acid. The organic solution was then neutralised with sodiumbicarbonate, dried over magnesium sulfate and concentrated under reducedpressure to give 4-hydroxymethyl-4′-nitrobenzophenone (2.08 g, 81%) as abeige solid.

Synthesis of 4-di(ethyleneglycol)benzyl ether-4′-nitrobenzophenone (4)

4-Hydroxymethyl-4′-nitrobenzophenone (3.00 g, 11.7 mmol, 1 eq) wasdissolved in THF (45 mL) and the yellow solution was cooled to 0° C. inan ice/water bath. The sodium hydride (0.70 g, 17.5 mmol, 1.5 eq, 60%dispersion) was added portionwise other 10 min turning the solution adark blue/black colour. The mixture was warmed to room temperature andstirred for 30 min. The mixture was cooled to 0° C. and2-(2-chloroethoxy)ethanol (1.48 mL, 14.0 mmol, 1.2 eq) was addeddropwise over 5 min turning the solution a dark orange colour. Theorange mixture was then allowed to warm to room temperature and stirredfor a further 18 h. After this time the reaction was quenched with asmall amount of water and the mixture was concentrated under reducedpressure to give an orange oil. The product was used in the next stepwithout further purification due to the difficult work up involved withmolecules such as this which exhibit surfactant properties.

Attachment of cyanuric chloride to 4-di(ethyleneglycol)benzylether-4′-nitrobenzophenone (5)

Cyanuric chloride (0.42 g, 2.3 mmol, 1.5 eq) and Hünig's base (0.63 mL,2.3 mmol, 1.5 eq) were dissolved in tetrahydrofuran (20 mL) and thecolourless solution was cooled to 0° C. A solution of4-di(ethyleneglycol)benzyl ether-4′-nitrobenzophenone (0.50 g, 1.5 mmol,1 eq) in tetrahydrofuran (5 mL) was added dropwise over 5 min to give anorange turbid mixture. The mixture was then allowed to warm to roomtemperature and stirred for 18 h. At this point HPLC showed that thestarting material had been consumed and so the precipitate was filteredoff. The filtrate was concentrated under reduced pressure to give anorange oil which was used in the next stage without furtherpurification.

Coupling of triazine-linked 4-di(ethyleneglycol)benzylether-4′-nitrobenzophenone to Locust bean gum (6)

The triazine-linked 4-di(ethyleneglycol)benzylether-4′-nitrobenzophenone (0.74 g, 1.5 mmol, 500 eq) was dissolved intetrahydrofuran (20 mL) and Hünig's base (0.32 mL, 1.8 mmol, 600 eq) wasadded to give an orange solution. Locust bean gum (1.00 g, 3 μmol, 1 eq)was added in one portion and the turbid mixture was heated to 50° C. Themixture was then stirred for 24 hr at which point HPLC indicated thatthere was no more starting material present in the reaction mixture. Thereaction was cooled and filtered to yield an orange solid. The solid waswashed with THF, dried and used in the next stage without furtherpurification.

Formation of Tosyl Hydrazone from the Locust Bean Gum-Triazine AttachedNitrobenzophenone (7)

The Locust bean gum-attached nitrobenzophenone (1.70 g, 1.5 mmol, 1 eq)was suspended in methanol (20 mL) and tosyl hydrazide (0.70 g, 3.8 mmol,2.5 eq) was added portionwise over 2 min. The suspension was then heatedto reflux for 24 hr and then allowed to cool to yield the product.

Route 2 Synthesis of Ether Linked Diazomethane Locust Bean Gum, withReference to FIG. 2 Attachment of Locust Bean Gum to4-bromomethyl-4′-nitro-benzophenone (9)

Locust bean gum (1.00 g, 3 μmol, 1 eq) was suspended in THF (20 mL) andthe beige suspension was cooled to 0° C. Sodium hydride (0.05 g, 3.12mmol, 106.0 eq, 60% dispersion) was added portionwise over 5 mins togive a brown suspension. The suspension was allowed to warm to roomtemperature and stirred for 10 mins. The suspension was then cooledagain to 0° C. and 4-bromomethyl-4′-nitro-benzophenone (1.00 g, 3.12mmol, 105.8 eq) was added slowly over 30 mins. The mixture was thenallowed to warm to room temperature and stirred for 18 hr. The reactionwas quenched carefully with water (0.5 mL) and the dark brown solid wasfiltered from the mixture. The solid was washed with methanol and driedin air to give a fine brown solid (2 g). This compound was then used inthe next step without further purification.

Formation of Tosyl Hydrazone from Ether Attached Locust Bean GumBenzophenone (10)

The benzophenone (2.00 g, 3.12 mmol, 1 eq) and tosyl hydrazide (1.45 g,7.80 mmol, 2.5 eq) were mixed in methanol (15 mL) to give a beigesuspension. The suspension was heated to reflux for 18 hr and thenallowed to cool. The suspension was then filtered and used directly inthe next step.

Synthesis of tris(4-methyl diaryldiazomethane) 1,3,5-benzene triester(19), with reference to FIG. 4

A solution of 1,3,5 benzene tricarbonyl trichloride 1 (2.33 g, 8.8=101)in DCM (10 mL) was cooled to 0° C. in an ice bath. DMAP (cat. 54 mg, 0.4mmol) and triethylamine (12.2 mL, 88 mmol) were added to the solutionand allowed to cool. Then hydroxymethyl benzophenone diazo 2 (6 g, 26mmol) in DCM (40 mL) was added and stirring maintained as the mixturewarmed to room temperature. After 4 hours there was no starting materialleft by TLC and the reaction was worked up by diluting with DCM (60 mL)and partitioning between DCM and brine. The combined organic layer (200mL) was dried with MgSO₄ filtered and concentrated in vacuo to yield 3(7.99 g, quant.) as a red solid; ν_(max) (thin film) 2010, 1720, 1220cm⁻¹.

Synthesis of 1,2,3-tri-O-(4-hydroxymethyl diaryldiazomethane-D,L-glyceryl ether (20), with reference to FIG. 5 Synthesisof 4-(1′,2′-O-isopropylidene-D,L-glyceryl)-methylbenzophenone (21)

To a solution of 1,2-O-isopropylidene-D,L-glycerol (1.0 eq) in THF (1ml/mmol) at 0° C. was added sodium hydride (60% dispersion, 1.25 eq).The mixture was stirred for 5 mins then quenched with4-bromomethylbenzophenone 2 (1.0 eq). The mixture was allowed to warm toroom temperature, stirred for 4 h, then diluted with water. The THF wasremoved in vacuo and the residue portioned between ethyl acetate andwater. The organic layer was collected and concentrated to yield theproduct 21 in a quantitative yield.

Synthesis of 4-(D,L-glyceryl)-methylbenzophenone (22)

A mixture of 4-(1′,2′-O-isopropylidene-D,L-glyceryl)-methylbenzophenone21 (1.0 eq) in acetic acid (1 ml/mmol) and water (1 ml/mmol) was heatedto 50° C. for 3.5 h after which the solvent was removed in vacuo. Theresidue was diluted with water and concentrated in vacuo a further 3times to remove trace acetic acid to afford a 22 (98%) as a colourlessoil.

Synthesis of 1,2,3-tri-O-(4-hydroxymethylbenzophenone)-D,L-glycerylether (23)

To a solution of 4-hydroxymethylbenzophenone-D,L-glyceryl ether 21 (1.0eq) in N,N-dimethylformamide (1 ml/mmol) at 0° C. was added sodiumhydride (60% dispersion, 2.4 eq). The mixture was stirred for 5 min thenquenched with 4-bromomethylbenzophenone 2 (2.0 eq) and allowed to warmto ambient temperature. After 18 h the mixture diluted with water andextracted with methyl tert-butyl ether. The organic extract was washedwith water and concentrated to yield 23 (76%) as a colourless oil.

Synthesis of 1,2,3-tri-O-(4-hydroxymethylbenzophenonehydrazone)-D,L-glyceryl ether (24)

To a solution of 1,2,3-tri-O-(4-hydroxymethylbenzophenone)-D,L-glycerylether 23 (1.0 eq) in propanol (1 ml/mmol) was added hydrazinemonohydrate (12 eq). The mixture was heated to reflux for 18 h thediluted ethyle actetae and water. The organic phase was collected,washed with water then concentrated to yield the product 24 (98%) as ayellow oil.

Synthesis of 1,2,3-tri-O-(4-hydroxymethyl diaryldiazomethane-D,L-glyceryl ether (20)

To a solution of 1,2,3-tri-O-(4-hydroxymethylbenzophenonehydrazone)-D,L-glyceryl ether 24 (1.0 eq) in tetrahydrofuran (2 ml/mmol)was added sodium sulfate (4 eq), a methanolic solution of potassiumhydroxide (1 ml/g, 6 eq) and yellow mercury oxide (3.3 eq). The mixturewas stirred for 18 h in the dark before being filtered to a pad ofCelite. The filtrate was concentrated in vacuo and the residue dissolvedin ethyl acetate and washed with water. The organic layer was collectedand concentrated to yield the product 20 (99%) as a dark red oil.

General Synthesis of Poly Tosylhydrazones with Reference to FIG. 6Synthesis of Benzophenone Modified Polymer (25)

A solution of polymer in a suitable solvent (nitroethane,dichloromethane, chloroform) was treated with 4-nitro benzoyl chloride(1 eq) and aluminium chloride (1.2 eq). The solution was stirred at roomtemperature or at 40° C. then quenched with water. The organic layer wascollected and washed with 1M HCl and 1M NaOH solutions sequentially.Concentration of the organic layer yielded the product.

Synthesis of Tosyl Hydrazone Modified Polymer (26)

A suspension of benzophenone polymer (25) in an organic solvent(nitroethane, toluene/methanol or chloroform/methanol) was treated withtosyl hydrazide) and heated to 60-70° C. The mixture was quenched withwater and the organic layer washed with 1MCl, collected and evaporatedto yield the product (26).

TABLE 1 Overview of modified polymer prepared Base polymer Mw % of Tosylhydrazone Sample Number Polystyrene 200 70% 27 Polystyrene 2000 25% 28Polystyrene 60000 12.4%   29 SEBS >2000  2% 30

Example 2 Attaching Hydrophilic Polymers onto 3-Dimensional Surfaces,with Reference to FIG. 3 Attachment to the LBG to a Fluorescent Particlewith Reference to FIG. 3

The functionalised Locust bean gum (100 mg) was suspended in methanol(15 mL) and triethylamine (0.5 mL) was added turning the yellowsuspension a bright orange colour. The solvent was then removed underreduced pressure to yield the product (11). The direct linkeddiazomethane-LBG (11) was mixed with the 10 micron diameter fluorescentparticles (1% w/w of polymer with regard to the particle) and sonicatedto ensure they were thoroughly mixed. The mixture was heated underreflux for 2 hr

Simulated Wash to Show Increased Deposition of Encapsulates onto CottonWool

The encapsulate suspension was added to a standard basic buffer (30 mL,0.1 M sodium carbonate/sodium hydrogen carbonate). The mixture wasshaken and divided into two vials. Cotton Wool was added to the firstvial and the mixture was shaken at 500 rpm for 45 mins to simulate themain wash cycle of a washing machine. The second vial was also shaken at500 rpm for 45 mins and after this time samples were taken from thevials and the absorbance of the mixture at 400 nm was measured using aVarian UV-vis spectrometer.

TABLE 2 Results of simulated wash, showing increased deposition ofencapsulates onto Cotton Sample % name deposition Control 17 12 32

Simulated Wash to Show Increased Deposition of Encapsulates onto CottonFabric with Reference to FIG. 9

The encapsulate suspension was added to a standard basic buffer (30 mL,0.1 M sodium carbonate/sodium hydrogen carbonate). The mixture wasshaken and divided into two vials. Cotton Fabric was added to the firstvial and the mixture was shaken at 500 rpm for 45 mins to simulate themain wash cycle of a washing machine. The second vial was also shaken at500 rpm for 45 mins and after this time samples were taken from theanalysed using a fluorescent microscope. The fabric sample that had beenexposed to modified particle showed considerably more fluorescence thenthat of the control sample

Example 3 Attachment of a Coating to a Surface Experiment 1

A layer of tris-diazo 19 dissolved in methyl ethyl ketone (3% w/w) wasapplied to the substrate using a grade 1 K bar and allowed to dry. Thena layer of poly(ethyleneimine) in methanol (50% w/w) was applied using agrade 1 K bar and allowed to dry. The sample was then heat cured in anoven at 120° C. for 10-15 mins.

Experiment 2

A mixture of tris-diazo 19 in methanol (6% w/w) and poly(ethyleneimine)in methanol (200% w/w) where mixed together then applied to thesubstrate using a grade 1 K bar and allowed to dry. The sample was heatcured in an oven at 120° C. for 10-15 mins.

Experiment 3

A layer of diazo dissolved in methyl ethyl ketone (1% w/w) was appliedto the substrate using a grade 1 K bar and allowed to dry. A mixture oftris-diazo 19 in methanol (1% w/w) and poly(ethyleneimine) in methanol(60% w/w) where mixed together then applied to the substrate using agrade 1 K bar and allowed to dry. The sample was heat cured in an ovenat 120° C. for 10-15 mins. allowed to dry. The sample was then heatcured in an oven at 120° C. for 10-15 mins.

Experiment 4

A mixture of tris-diazo 20 in methanol (6% w/w) and poly(ethyleneimine)in methanol (200% w/w) where mixed together then applied to thesubstrate using a grade 1 K bar and allowed to dry. The sample was heatcured in an oven at 120° C. for 10-15 mins.

Experiment 5

A layer of diazo dissolved in methyl ethyl ketone (1% w/w) was appliedto the substrate using a grade 1 K bar and allowed to dry. A mixture oftris-diazo 20 in methanol (1% w/w) and poly(ethyleneimine) in methanol(60% w/w) where mixed together then applied to the substrate using agrade 1 K bar and allowed to dry. The sample was heat cured in an ovenat 120° C. for 10-15 mins.

TABLE 3 Results of Experiments 1 to 5 Substrate Poly(ethylene Biaxialorientated terephthalate), Water polypropylene, Water Contact angleContact angle Untreated 66° 72° Experiment 1 56° 23° Experiment 2 25°26° Experiment 3 27° 25° Experiment 4 40° 39° Experiment 5 59° 50°

Example 4 Network Formation of Polymers Via Solution Process Experiment6

To a solution of polyethylene imine in methyl ethyl ketone was added asample of chemical agent. The mixture was stirred until a solution wasformed then cast onto a PTFE sheet. The resulting film was cured at a140° C. for 15 mins, cooled then examined.

TABLE 4 Results of Experiments 6 Chemical Agent Apperence after cureNone Thick oil 19 Solid 27 Solid 28 Solid

Example 5 Network Formation of Polymers Coating Via Hot Melt ProcessExperiment 7

To a mixture of Elvax 150 (65 eq w/w) and Picolastic A5 (35 eq w/w) wasadded chemical agent (27) (3 eq w/w) and the sample heated to 100° C.with mixing until a homogenous mixture was obtained. The mixture wascooled and DBU was added (3 eq w/w) slowly. The mixture was warmed to100° C. then stirred until a homogenous red colour was achieved throughout the mixture. The mixture was then heated to 150° C. for XX thencooled. The viscosity of sample was measured using a brookfiledviscometer at 120° c., a shear rate of and a equilibration time of 1 hr.

TABLE 5 Results of Experiments 7 Chemical Agent Cure % Viscosity NonePre Cure 70 None Pre Cure 70 27 Post Cure 70 27 Post Cure >100% 

Experiment 8

To a solution of chemical agent (27) (3 eq w/w) in methanol/MEK wasadded LiOH (3 eq w/w). The mixture was stirred the concentrated in vacuoto yield a red solid. This red solid was added to a mixture of Elvax 150(65 eq w/w) and Picolastic A5 (35 eq w/w) and the sample heated to 100°C. with mixing until a homogenous mixture was obtained. The mixture wasthen heated to 150° C. for XX then cooled. The viscosity of sample wasmeasured using a brookfiled viscometer at 120° c., a shear rate of 0.3rpm and an equilibration time of 1 hr.

TABLE 5 Results of Experiments 7 Chemical Agent Cure % Viscosity* NonePre Cure 50-60 None Pre Cure 50-60 27 Post Cure 50-60 27 Post Cure >100%

Example 5 Network Formation Between a Coating and Two SubstratesExperiment 9 Solution Based Processing

To a solution of polymer in toluene (20 wt %) was added triethylamine(5% w/w wrt polymer chemical agent 27 or 19 (5% w/w wrt polymer) and themixture stirred until a solution was formed. This solution was appliedto an FR-4 C stage expoy board using a “k-bar” to achieve a 150 micronwet film thickness. A second sheet of FR4 epoxy resin is the applied tothe adhesive and the sandwich is the clamped and heated to 150° C. for 2h before being allowed to cool for 24 h. The adhesive strength isobtained using a T-Peel configuration. (Table 6)

TABLE 6 Results of Experiments 9 Chemical T-Peel Strength Agent PolymerN/cm None Kraton 1102 2.6 19 Kraton 1102 5.6 27 Kraton 1102 9.1 NoneKraton 1153 2.7 27 Kraton 1153 7.4 None Kraton 1184 5.7 27 Kraton 11847.7 None Kraton 1652 1.3 27 Kraton 1652 8.5 None Kraton 1111 3.3 27Kraton 1111 4.5

Experiment 10 Dry Film Based Processing

To a solution of polymer in toluene (20 wt %) was added triethylamine(5% w/w wrt polymer chemical agent 27 (5% w/w wrt polymer) and themixture stirred until a solution was formed. This solution was coatedonto a PTFE sheet and allowed to dry. The resulting dry film was appliedto an FR-4 C stage expoy board. A second sheet of FR4 epoxy resin is theapplied to the adhesive and the sandwich is the clamped and heated to150° C. for 2 h before being allowed to cool for 24 h. The adhesivestrength is obtained using a T-Peel configuration. (Table 10)

TABLE 7 Results of Experiments 10 Chemical T-Peel Strength Agent PolymerN/cm None Kraton 1102 2.6 27 Kraton 1102 9.2

The invention claimed is:
 1. A functionalised compound of formula (II),which functionalised compound comprises carbene precursor groups whichare the same or different, wherein n is an integer equal to or greaterthan 3:

wherein x is 1, E is a group which is capable of being converted into acarbene reactive intermediate group, Q is a core moiety, a polymer or adendrimer, and each of the [R]_(x)-E-L- groups, which are the same ordifferent, is independently selected from a group of formula (Ie) and agroup of formula (Ia):

wherein R is aryl or heteroaryl, which aryl is a monocyclic or bicyclicaromatic group, and which aryl or heteroaryl is unsubstituted orsubstituted by one or two groups, which groups are the same or differentand are independently selected from C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, aryl,cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy, haloalkyl,thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl, sulfonamide,tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl, diaryl(C₁₋₂₀alkyl)silyl and triarylsilyl; each L, which is the same or different, isa single bond or a group of formula (XII)

wherein: A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene; A² is a single bond or an unsubstituted or substitutedgroup selected from C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene,heteroarylene, *—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1to 20, *—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and A³ is a single bond or an unsubstituted orsubstituted group selected from *—Z²-arylene, *—Z²-heteroarylene,*—Z²—C₁₋₂₀ alkylene, arylene, heteroarylene, C₁₋₂₀ alkylene,*—Z²-arylene-O, heteroarylene-O, *—Z²—C₁₋₂₀ alkylene-O, *-arylene-O,*-heteroarylene-O, *—C₁₋₂₀ alkylene-O, C(O), S(O)₂, *—OC(O),*—N(R″)C(O), O, S, N(R″), *—C(O)O, *—C(O)N(R″), *—S(O)₂O, C₁₋₂₀alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀ alkenylene and *—Z²—C₁₋₂₀alkynylene, wherein Z² is selected from O, S, N(R″), C(O), S(O), S(O)₂,C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ is independentlyselected from H, C₁₋₆ alkyl and aryl, and wherein * is the point ofattachment of A³ to A²; R¹ is —S(O)₂R² or H, wherein R² is anunsubstituted or substituted C₁₋₆ alkyl group or an unsubstituted orsubstituted aryl group; wherein said core moiety, polymer or dendrimercomprises n linker groups of formula A⁴, each of which is attached to L,wherein n is an integer equal to or greater than 3; each A⁴ is the sameor different and is independently selected from a single bond,—Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀ alkylene-*, arylene,heteroarylene, C₁₋₂₀ alkylene, —Z³-arylene-O—*, —Z³-heteroarylene-O—*,—Z³—C₁₋₂₀ alkylene-O—*, arylene-O—*, heteroarylene-O—*, C₁₋₂₀alkylene-O—*, —C(O)—*, S(O)₂, —OC(O)—*, —N(R″)C(O)—*, O, S, N(R″),—C(O)O—*, —C(O)N(R″)—*, —S(O)₂O—*, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene,—Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀ alkynylene-*, wherein Z³ isselected from O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″)and N(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl, and wherein * is the point of attachment of A⁴ to L;said core moiety is a straight-chained or branched, saturated orunsaturated C₁₋₂₀ hydrocarbon moiety; an aryl ring; a heteroaryl ring; aC₅₋₁₀ carbocyclic ring; a C₅₋₁₀ heterocyclic ring; or a fused bi-, tri-or tetracyclic ring system wherein each ring of said fused bi-, tri- ortetracyclic ring system is independently selected from an aryl ring, aheteroaryl ring, a C₅₋₁₀ carbocyclic ring and a C₅₋₁₀ heterocyclic ring;wherein said hydrocarbon moiety, aryl ring, heteroaryl ring, carbocyclicring, heterocyclic ring or fused bi-, tri- or tetracyclic ring system issubstituted with said n linker groups, A⁴, and is or is not substitutedwith one or more groups other than said n linker groups, A⁴; and saiddendrimer is (a) a poly(amidoamine) (PAMAM) dendrimer or (b) a dendrimerwhich comprises from 50 to 500 surface groups which are linker groups offormula A⁴; with the proviso that when none of the [R]_(x)-E-L- groupsis a group of formula (Ie) in which R¹ is —S(O)₂R², then: each L is agroup of formula (XII); and Q is a core moiety, a dendrimer, or apolymer, which polymer comprises: a polysaccharide, a protein, apolyester, a polyether, a polyacrylate, a polymethacrylate, apolycarbonate, polyetheretherketone (PEEK), a polyetherimide, apolyimide, a polysulfone, poly(vinyl chloride), a polysilane, apolysiloxane, a polyurea, a polyurethane, polylactic acid,polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or asalt thereof.
 2. The functionalised compound according to claim 1 whichis a hydrazone compound of formula (XXX)

wherein: n is an integer equal to or greater than 3; R is aryl orheteroaryl, which aryl is a monocyclic or bicyclic aromatic group, andwhich aryl or heteroaryl is unsubstituted or substituted by one or twogroups, which groups are the same or different and are independentlyselected from C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, aryl, cyano, nitro,hydroxy, halo, carboxy, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, acyl, acyloxy, acylamido,ester, C₁₋₁₀ alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio,arylthio, sulfonic acid, sulfonyl, sulfonamide, tri(C₁₋₂₀ alkyl)silyl,aryldi(C₁₋₂₀ alkyl)silyl, diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl;each L, which is the same or different, is a single bond or a group offormula (XII)

wherein: A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene; A² is a single bond or an unsubstituted or substitutedgroup selected from C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene,heteroarylene, *—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1to 20, *—Z¹C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and A³ is a single bond or an unsubstituted orsubstituted group selected from *—Z²-arylene, *—Z²-heteroarylene,*—Z²—C₁₋₂₀ alkylene, arylene, heteroarylene, C₁₋₂₀ alkylene,*—Z²-arylene-O, *—Z²-heteroarylene-O, *—Z²—C₁₋₂₀ alkylene-O,*-arylene-O, *-heteroarylene-O, *—C₁₋₂₀ alkylene-O, C(O), S(O)₂,*—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O, *—C(O)N(R″), *—S(O)₂O, C₁₋₂₀alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀ alkenylene and *—Z²—C₁₋₂₀alkynylene, wherein Z² is selected from O, S, N(R″), C(O), S(O), S(O)₂,C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ is independentlyselected from H, C₁₋₆ alkyl and aryl, and wherein * is the point ofattachment of A³ to A²; R¹ is H or —S(O)₂R², wherein R² is anunsubstituted or substituted C₁₋₆ alkyl group or an unsubstituted orsubstituted aryl group; Q is a core moiety, a polymer or a dendrimer,which core moiety, polymer or dendrimer comprises n linker groups offormula A⁴, each of which is attached to L, wherein n is an integerequal to or greater than 3; each A⁴ is the same or different and isindependently selected from a single bond, —Z³-arylene-*,—Z³-heteroarylene-*, —Z³—C₁₋₂₀ alkylene-*, arylene, heteroarylene, C₁₋₂₀alkylene, —Z³-arylene-O—*, —Z³-heteroarylene-O—*, —Z³—C₁₋₂₀alkylene-O—*, arylene-O—*, heteroarylene-O—*, C₁₋₂₀ alkylene-O—*,—C(O)—*, S(O)₂, —OC(O)—*, —N(R″)C(O)—*, O, S, N(R″), —C(O)O—*,—C(O)N(R″)—*, —S(O)₂O—*, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene, —Z³—C₁₋₂₀alkenylene-* and —Z³—C₁₋₂₀ alkynylene-*, wherein Z³ is selected from O,S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O),wherein each R″ is independently selected from H, C₁₋₆ alkyl and aryl,and wherein * is the point of attachment of A⁴ to L; said core moiety isa straight-chained or branched, saturated or unsaturated C₁₋₂₀hydrocarbon moiety; an aryl ring; a heteroaryl ring; a C₅₋₁₀ carbocyclicring; a C₅₋₁₀ heterocyclic ring; or a fused bi-, tri- or tetracyclicring system wherein each ring of said fused bi-, tri- or tetracyclicring system is independently selected from an aryl ring, a heteroarylring, a C₅₋₁₀ carbocyclic ring and a C₅₋₁₀ heterocyclic ring; whereinsaid hydrocarbon moiety, aryl ring, heteroaryl ring, carbocyclic ring,heterocyclic ring or fused bi-, tri- or tetracyclic ring system issubstituted with said n linker groups, A⁴, and is or is not substitutedwith one or more groups other than said n linker groups, A⁴; and saiddendrimer is (a) a poly(amidoamine) (PAMAM) dendrimer or (b) a dendrimerwhich comprises from 50 to 500 surface groups which are linker groups offormula A⁴; with the proviso that when R¹ is H, then: each L is a groupof formula (XII); and Q is a core moiety, a dendrimer, or a polymer,which polymer comprises: a polysaccharide, a protein, a polyester, apolyether, a polyacrylate, a polymethacrylate, a polycarbonate,polyetheretherketone (PEEK), a polyetherimide, a polyimide, apolysulfone, poly(vinyl chloride), a polysilane, a polysiloxane, apolyurea, a polyurethane, polylactic acid, polyvinylidene chloride, afluoro-polymer, a polyethylene imine, or a salt thereof.
 3. Thefunctionalised compound according to claim 1 which is asulfonylhydrazone compound of formula (XXXa)

wherein: n is an integer equal to or greater than 3; R is aryl orheteroaryl, which aryl is a monocyclic or bicyclic aromatic group, andwhich aryl or heteroaryl is unsubstituted or substituted by one or twogroups, which groups are the same or different and are independentlyselected from C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, aryl, cyano, nitro,hydroxy, halo, carboxy, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, acyl, acid, sulfonyl,sulfonamide, tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl,diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl; each L, which is the same ordifferent, is a single bond or a group of formula (XII)

wherein: A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene; A² is a single bond or an unsubstituted or substitutedgroup selected from C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene,heteroarylene, *—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1to 20, *—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and A³ is a single bond or an unsubstituted orsubstituted group selected from *—Z²-arylene, *—Z²-heteroarylene,*—Z²—C₁₋₂₀ alkylene, arylene, heteroarylene, C₁₋₂₀ alkylene,*—Z²-arylene-O, *—Z²-heteroarylene-O, *—Z²—C₁₋₂₀ alkylene-O,*-arylene-O, *-heteroarylene-O, *—C₁₋₂₀ alkylene-O, C(O), S(O)₂,*—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O, *—C(O)N(R″), *—S(O)₂O, C₁₋₂₀alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀ alkenylene and *—Z²—C₁₋₂₀alkynylene, wherein Z² is selected from O, S, N(R″), C(O), S(O), S(O)₂,C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ is independentlyselected from H, C₁₋₆ alkyl and aryl, and wherein * is the point ofattachment of A³ to A²; R² is an unsubstituted or substituted C₁₋₆ alkylgroup or an unsubstituted or substituted aryl group; Q is a core moiety,a polymer or a dendrimer, which core moiety, polymer or dendrimercomprises n linker groups of formula A⁴, each of which is attached to L,wherein n is an integer equal to or greater than 3; each A⁴ is the sameor different and is independently selected from a single bond,—Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀ alkylene-*, arylene,heteroarylene, C₁₋₂₀ alkylene, —Z³-arylene-O—*, —Z³-heteroarylene-O—*,—Z³—C₁₋₂₀ alkylene-O—*, arylene-O—*, heteroarylene-O—*, C₁₋₂₀alkylene-O—*, —C(O)—*, S(O)₂, —OC(O)—*, —N(R″)C(O)—*, O, S, N(R″),—C(O)O—*, —C(O)N(R″)—*, —S(O)₂O—*, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene,—Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀ alkynylene-*, wherein Z³ isselected from O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″)and N(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl, and wherein * is the point of attachment of A⁴ to L;said core moiety is a straight-chained or branched, saturated orunsaturated C₁₋₂₀ hydrocarbon moiety; an aryl ring; a heteroaryl ring; aC₅₋₁₀ carbocyclic ring; a C₅₋₁₀ heterocyclic ring; or a fused bi-, tri-or tetracyclic ring system wherein each ring of said fused bi-, tri- ortetracyclic ring system is independently selected from an aryl ring, aheteroaryl ring, a C₅₋₁₀ carbocyclic ring and a C₅₋₁₀ heterocyclic ring;wherein said hydrocarbon moiety, aryl ring, heteroaryl ring, carbocyclicring, heterocyclic ring or fused bi-, tri- or tetracyclic ring system issubstituted with said n linker groups, A⁴, and is or is not substitutedwith one or more groups other than said n linker groups, A⁴; and saiddendrimer is (a) a poly(amidoamine) (PAMAM) dendrimer or (b) a dendrimerwhich comprises from 50 to 500 surface groups which are linker groups offormula A⁴.
 4. The functionalised compound according to claim 1 whereinL is a single bond, and Q comprises at least n aryl or heteroaryl rings,wherein n is an integer equal to or greater than 3, wherein each L whichis single bond is attached directly to said aryl or heteroaryl ring,thereby bonding the aryl or heteroaryl ring directly to the carbon atomof E which is bonded to R.
 5. The functionalised compound according toclaim 1 wherein: (a) Q comprises polystyrene, a copolymer comprisingpolystyrene, a thermoplastic elastomer, polyisoprene, a copolymercomprising polyisoprene, SBS rubber, SIS rubber orpoly(styrene)-poly(ethylene/butylene)-poly(styrene) (SEBS); or (b) Q isa core moiety of formula (XIV), which core moiety comprises n linkergroups of formula A⁴, each of which is attached to L, wherein n is aninteger from 3 to 10:

wherein each A⁴ is the same or different and is independently selectedfrom a single bond, —Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀alkylene-*, arylene, heteroarylene, C₁₋₂₀ alkylene, —Z³-arylene-O—*,—Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ alkylene-O—*, arylene-O—*,heteroarylene-O—*, C₁₋₂₀ alkylene-O—*, —C(O)—*, S(O)₂, —OC(O)—*,—N(R″)C(O)—*, O, S, N(R″), —C(O)O—*, —C(O)N(R″)—*, —S(O)₂O—*, C₁₋₂₀alkenylene, C₁₋₂₀ alkynylene, —Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀alkynylene-*, wherein Z³ is selected from O, S, N(R″), C(O), S(O),S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ isindependently selected from H, C₁₋₆ alkyl and aryl, and wherein * is thepoint of attachment of A⁴ to L, and wherein A is an aryl ring, aheteroaryl ring, a C₅₋₁₀ carbocyclic ring, a C₅₋₁₀ heterocyclic ring, ora fused bi-, tri- or tetracyclic ring system wherein each ring of saidfused bi-, tri- or tetracyclic ring system is independently selectedfrom an aryl ring, a heteroaryl ring, a C₅₋₁₀ carbocyclic ring and aC₅₋₁₀ heterocyclic ring; or (c) Q is a core moiety of formula (XVI),which core moiety comprises n linker groups of formula A⁴, each of whichis attached to L, wherein n is an integer from 3 to 10:

wherein each A⁴ is the same or different and is independently selectedfrom a single bond, —Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀alkylene-*, arylene, heteroarylene, C₁₋₂₀ alkylene, —Z³-arylene-O—*,—Z³-heteroarylene-O—*, —Z³—C₁₋₂₀ alkylene-O—*, arylene-O—*,heteroarylene-O—*, C₁₋₂₀ alkylene-O—*, —C(O)—*, S(O)₂, —OC(O)—*,—N(R″)C(O)—*, O, S, N(R″), —C(O)O—*, —C(O)N(R″)—*, —S(O)₂O— * , C₁₋₂₀alkenylene, C₁₋₂₀ alkynylene, —Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀alkynylene-*, wherein Z³ is selected from O, S, N(R″), C(O), S(O),S(O)₂, C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ isindependently selected from H, C₁₋₆ alkyl and aryl, and wherein * is thepoint of attachment of A⁴ to L, and wherein A^(HC) is straight-chainedor branched, saturated or unsaturated C₁₋₂₀ hydrocarbon moiety which issubstituted with said n linker groups, A⁴, and is or is not substitutedwith one or more groups other than said n linker groups, A⁴.
 6. A methodfor the use of a functionalised compound as defined in claim 1 as anagent for producing a chemically-bound three-dimensional network on orwithin a substrate, or as a cross linking agent.
 7. A process forproducing a chemically-bound three-dimensional network on or within asubstrate, which process comprises: (a) contacting a substrate with afunctionalised compound as defined in claim 1; and (b) generatingcarbene reactive intermediate groups from said carbene precursor groups,so that said carbene reactive intermediate groups react with thesubstrate to produce said chemically-bound three-dimensional network onor within the substrate.
 8. A process for producing a chemically-boundthree-dimensional network between a first substrate and a secondsubstrate, which process comprises: (a) contacting a first substrate anda second substrate with a functionalised compound as defined in claim 1;and (b) generating carbene reactive intermediate groups from saidcarbene precursor groups, so that said carbene reactive intermediategroups react with the first substrate and the second substrate toproduce said chemically-bound three-dimensional network between saidfirst and second substrates.
 9. A process for producing a film or acoating, which process comprises: (a) disposing a film formulation or acoating formulation onto the surface of a substrate, which film orcoating formulation comprises a functionalised compound as defined inclaim 1; and (b) generating carbene reactive intermediate groups fromsaid carbene precursor groups, thereby forming a film or a coating onsaid substrate.
 10. A process for producing a treated particle, whichprocess comprises: (a) contacting a functionalised cross linkingcompound with a substrate particle, wherein the functionalised crosslinking compound is a compound as defined in claim 1; and (b) generatingcarbene reactive intermediate groups from said carbene precursor groups,so that a carbene reactive intermediate group reacts with the substrateparticle to attach the particle to the compound, thereby yielding saidtreated particle.
 11. A process for cross linking a first substrate to asecond substrate, which first and second substrates are the same ordifferent, which process comprises (a) contacting the first and secondsubstrates with a functionalised cross linking compound, wherein thefunctionalised cross linking compound is a compound as defined in claim1; and (b) generating carbene reactive intermediate groups from saidcarbene precursor groups, so that at least one carbene reactiveintermediate group reacts with the first substrate and at least oneother reactive intermediate group reacts with the second substrate,thereby cross linking the first and second substrates.
 12. A process forproducing a functionalised compound of formula (II), whichfunctionalised compound comprises carbene precursor groups which are thesame or different, wherein n is an integer equal to or greater than 3:

wherein x is 1, E is a group which is capable of being converted into acarbene reactive intermediate group, Q is a core moiety, a polymer or adendrimer, and each of the [R]_(x)-E-L- groups, which are the same ordifferent, is independently selected from a group of formula (Ie) and agroup of formula (Ia):

wherein R is aryl or heteroaryl, which aryl is a monocyclic or bicyclicaromatic group, and which aryl or heteroaryl is unsubstituted orsubstituted by one or two groups, which groups are the same or differentand are independently selected from C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀alkynyl, C₁₋₂₀ haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, aryl,cyano, nitro, hydroxy, halo, carboxy, amino, C₁₋₁₀ alkylamino,di(C₁₋₁₀)alkylamino, arylamino, diarylamino, arylalkylamino, amido,acyl, acyloxy, acylamido, ester, C₁₋₁₀ alkoxy, aryloxy, haloalkyl,thiol, C₁₋₁₀ alkylthio, arylthio, sulfonic acid, sulfonyl, sulfonamide,tri(C₁₋₂₀ alkyl)silyl, aryldi(C₁₋₂₀ alkyl)silyl, diaryl(C₁₋₂₀alkyl)silyl and triarylsilyl; each L, which is the same or different, isa single bond or a group of formula (XII)

wherein: A¹ is bonded to the carbon atom bonded to R, wherein A¹ is anunsubstituted or substituted group selected from arylene andheteroarylene; A² is a single bond or an unsubstituted or substitutedgroup selected from C₁₋₂₀ alkylene, C₁₋₂₀ perfluoroalkylene, arylene,heteroarylene, *—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m) wherein m is 1to 20, *—Z¹—C₁₋₂₀ alkylene, *—Z¹—C₁₋₂₀ perfluoroalkylene, *—Z¹-arylene,*—Z¹-heteroarylene and *—Z¹—C₁₋₂₀ alkylene-(O—C₁₋₂₀ alkylene-)_(m)wherein m is 1 to 20, wherein Z¹ is selected from O, S, C(O), S(O),S(O)₂, N(R″), C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein * is thepoint of attachment of A² to A¹, wherein each of said C₁₋₂₀ alkylene andC₁₋₂₀ perfluoroalkylene groups is optionally interrupted by N(R″), O, Sor arylene, and wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl; and A³ is a single bond or an unsubstituted orsubstituted group selected from *—Z²-arylene, *—Z²-heteroarylene,*—Z²—C₁₋₂₀ alkylene, arylene, heteroarylene, C₁₋₂₀ alkylene,*—Z²-arylene-O, *—Z²-heteroarylene-O, *—Z²—C₁₋₂₀ alkylene-O,*-arylene-O, *-heteroarylene-O, *—C₁₋₂₀ alkylene-O, C(O), S(O)₂,*—OC(O), *—N(R″)C(O), O, S, N(R″), *—C(O)O, *—C(O)N(R″), *—S(O)₂O, C₁₋₂₀alkenylene, C₁₋₂₀ alkynylene, *—Z²—C₁₋₂₀ alkenylene and *—Z²—C₁₋₂₀alkynylene, wherein Z² is selected from O, S, N(R″), C(O), S(O), S(O)₂,C(O)O, OC(O), C(O)N(R″) and N(R″)C(O), wherein each R″ is independentlyselected from H, C₁₋₆ alkyl and aryl, and wherein * is the point ofattachment of A³ to A²; R¹ is —S(O)₂R² or H, wherein R² is anunsubstituted or substituted C₁₋₆ alkyl group or an unsubstituted orsubstituted aryl group; wherein said core moiety, polymer or dendrimercomprises n linker groups of formula A⁴, each of which is attached to L,wherein n is an integer equal to or greater than 3, each A⁴ is the sameor different and is independently selected from a single bond,—Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀ alkylene-*, arylene,heteroarylene, C₁₋₂₀ alkylene, —Z³-arylene-O—*, —Z³-heteroarylene-O—*,—Z³—C₁₋₂₀ alkylene-O—*, arylene-O—*, heteroarylene-O—*, C₁₋₂₀alkylene-O—*, —C(O)—*, S(O)₂, —OC(O)—*, —N(R″)C(O)—*, O, S, N(R″),—C(O)O—*, —C(O)N(R″)—*, —S(O)₂O—*, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene,—Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀ alkynylene-*, wherein Z³ isselected from O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″)and N(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl, and wherein * is the point of attachment of A⁴ to L;said core moiety is a straight-chained or branched, saturated orunsaturated C₁₋₂₀ hydrocarbon moiety; an aryl ring; a heteroaryl ring; aC₅₋₁₀ carbocyclic ring; a C₅₋₁₀ heterocyclic ring; or a fused bi-, tri-or tetracyclic ring system wherein each ring of said fused bi-, tri- ortetracyclic ring system is independently selected from an aryl ring, aheteroaryl ring, a C₅₋₁₀ carbocyclic ring and a C₅₋₁₀ heterocyclic ring;wherein said hydrocarbon moiety, aryl ring, heteroaryl ring, carbocyclicring, heterocyclic ring or fused bi-, tri- or tetracyclic ring system issubstituted with said n linker groups, A⁴, and is or is not substitutedwith one or more groups other than said n linker groups, A⁴; and saiddendrimer is (a) a poly(amidoamine) (PAMAM) dendrimer or (b) a dendrimerwhich comprises from 50 to 500 surface groups which are linker groups offormula A⁴; with the proviso that when none of the [R]_(x)-E-L- groupsis a group of formula (Ie) in which R¹ is —S(O)₂R², then: each L is agroup of formula (XII); and Q is a core moiety, a dendrimer, or apolymer, which polymer comprises: a polysaccharide, a protein, apolyester, a polyether, a polyacrylate, a polymethacrylate, apolycarbonate, polyetheretherketone (PEEK), a polyetherimide, apolyimide, a polysulfone, poly(vinyl chloride), a polysilane, apolysiloxane, a polyurea, a polyurethane, polylactic acid,polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or asalt thereof; which process comprises: (a) treating a first compound,Q′, which is a core moiety, a polymer or a dendrimer and which bears nfunctional groups, wherein n is an integer equal to or greater than 3,with at least one second compound of formula (VIa)

wherein: L′ is a leaving group or a reactive precursor to said group offormula (XII), wherein L′ is reactable with a said functional group tocouple the second compound to the first compound, R is aryl orheteroaryl, which aryl is a monocyclic or bicyclic aromatic group, andwhich aryl or heteroaryl is unsubstituted or substituted by one or twogroups, which groups are the same or different and are independentlyselected from C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀haloalkyl, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, aryl, cyano, nitro,hydroxy, halo, carboxy, amino, C₁₋₁₀ alkylamino, di(C₁₋₁₀)alkylamino,arylamino, diarylamino, arylalkylamino, amido, acyl, acyloxy, acylamido,ester, C₁₋₁₀ alkoxy, aryloxy, haloalkyl, thiol, C₁₋₁₀ alkylthio,arylthio, sulfonic acid, sulfonyl, sulfonamide, tri(C₁₋₂₀ alkyl)silyl,aryldi(C₁₋₂₀ alkyl)silyl, diaryl(C₁₋₂₀ alkyl)silyl and triarylsilyl, Yis N═N, O or N—NHR¹, wherein R¹ is H or —S(O)₂R² and wherein R² is anunsubstituted or substituted C₁₋₆ alkyl group or an unsubstituted orsubstituted aryl group, the n functional groups of said first compoundQ′ are groups of formula -A⁴-X², wherein each A⁴ is the same ordifferent and is independently selected from a single bond,—Z³-arylene-*, —Z³-heteroarylene-*, —Z³—C₁₋₂₀ alkylene-*, arylene,heteroarylene, C₁₋₂₀ alkylene, —Z³-arylene-O—*, —Z³-heteroarylene-O—*,—Z³—C₁₋₂₀ alkylene-O—*, arylene-O—*, heteroarylene-O—*, C₁₋₂₀alkylene-O—*, —C(O)—*, S(O)₂, —OC(O)—*, —N(R″)C(O)—*, O, S, N(R″),—C(O)O—*, —C(O)N(R″)—*, —S(O)₂O—*, C₁₋₂₀ alkenylene, C₁₋₂₀ alkynylene,—Z³—C₁₋₂₀ alkenylene-* and —Z³—C₁₋₂₀ alkynylene-*, wherein Z³ isselected from O, S, N(R″), C(O), S(O), S(O)₂, C(O)O, OC(O), C(O)N(R″)and N(R″)C(O), wherein each R″ is independently selected from H, C₁₋₆alkyl and aryl, and wherein * is the point of attachment of A⁴ to X², X²is H, a halo group or a leaving group, provided that when A⁴ is a singlebond, arylene, heteroarylene, C₁₋₂₀ alkylene, —Z²-arylene-*,—Z²-heteroarylene-*, —Z²—C₁₋₂₀ alkylene-* or S(O)₂, X² is other than Hand provided that when A⁴ is O, S, N(R″), —C(O)O—*, —C(O)N(R″)—*,—S(O)₂O—*, —Z³-arylene-O—*, —Z³-heteroarylene-O—*, —Z³⁻C₁₋₂₀alkylene-O—*, arylene-O—*, heteroarylene-O—* or C₁₋₂₀ alkylene-O—*, X²is other than a halo group, and said core moiety Q′ is astraight-chained or branched, saturated or unsaturated C₁₋₂₀ hydrocarbonmoiety; an aryl ring; a heteroaryl ring; a C₅₋₁₀ carbocyclic ring; aC₅₋₁₀ heterocyclic ring; or a fused bi-, tri- or tetracyclic ring systemwherein each ring of said fused bi-, tri- or tetracyclic ring system isindependently selected from an aryl ring, a heteroaryl ring, a C₅₋₁₀carbocyclic ring and a C₅₋₁₀ heterocyclic ring; wherein said hydrocarbonmoiety, aryl ring, heteroaryl ring, carbocyclic ring, heterocyclic ringor fused bi-, tri- or tetracyclic ring system is substituted with said nfunctional groups, -A⁴-X², and is or is not substituted with one or moregroups other than said n functional groups, -A⁴-X², provided that whennone of the [R]_(x)-E-L- groups in the functionalised compound offormula (II) to be produced is a group of formula (Ie) in which R¹ is—S(O)₂R², then each L′ is a reactive precursor to said group of formula(XII) and Q′ is said core moiety, said dendrimer, or said polymer, whichpolymer comprises: a polysaccharide, a protein, a polyester, apolyether, a polyacrylate, a polymethacrylate, a polycarbonate,polyetheretherketone (PEEK), a polyetherimide, a polyimide, apolysulfone, poly(vinyl chloride), a polysilane, a polysiloxane, apolyurea, a polyurethane, polylactic acid, polyvinylidene chloride, afluoro-polymer, a polyethylene imine, or a salt thereof; therebyproducing a third compound of formula (IXa):

wherein Q, L, R, Y and n are as defined above; provided that: when Y isO, the process further comprises: (b1) treating the third compound withH₂N—NHR¹ in the presence of heat, wherein R¹ is as defined above,thereby producing a fourth compound of formula (X):

wherein Q, L, R, R¹ and n are as defined above; and, optionally, (c1)converting some or all of the N—NHR¹ groups of said fourth compound intodiazo groups, N═N; and provided that: when Y is N—NHR¹, the processoptionally further comprises: (b2) converting some or all of the Ygroups of said third compound into diazo groups; thereby producing saidfunctionalised compound of formula (II).
 13. The functionalised compoundaccording to claim 1, wherein Q is a polymer or a core moiety.
 14. Thefunctionalised compound according to claim 1, wherein Q is a polymer.15. The functionalised compound according to claim 3, wherein Q is apolymer or a core moiety.
 16. The functionalised compound according toclaim 3, wherein Q is a polymer.